GB2259701A - Complexes of metallated organic molecules comprising multiple or mixed metallic species - Google Patents
Complexes of metallated organic molecules comprising multiple or mixed metallic species Download PDFInfo
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- GB2259701A GB2259701A GB9119871A GB9119871A GB2259701A GB 2259701 A GB2259701 A GB 2259701A GB 9119871 A GB9119871 A GB 9119871A GB 9119871 A GB9119871 A GB 9119871A GB 2259701 A GB2259701 A GB 2259701A
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- metal
- complex
- coordination complex
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 94
- 239000002184 metal Substances 0.000 claims abstract description 94
- 239000003446 ligand Substances 0.000 claims abstract description 34
- 150000001768 cations Chemical class 0.000 claims abstract description 28
- 150000001450 anions Chemical class 0.000 claims abstract description 20
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 18
- 239000002879 Lewis base Substances 0.000 claims abstract description 17
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- -1 2-mercaptobenzoxazolyl Chemical group 0.000 claims description 13
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 13
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910000510 noble metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- YZBBUYKPTHDZHF-KNVGNIICSA-N (3R)-7,2'-dihydroxy-4'-methoxyisoflavanol Chemical compound OC1=CC(OC)=CC=C1[C@H]1C(O)C2=CC=C(O)C=C2OC1 YZBBUYKPTHDZHF-KNVGNIICSA-N 0.000 claims 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims 1
- 229960004132 diethyl ether Drugs 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 7
- 239000000460 chlorine Substances 0.000 abstract description 4
- 229910002651 NO3 Inorganic materials 0.000 abstract 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 241000894007 species Species 0.000 description 5
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 229910002666 PdCl2 Inorganic materials 0.000 description 3
- 229910019032 PtCl2 Inorganic materials 0.000 description 3
- 241001061127 Thione Species 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000058 selane Inorganic materials 0.000 description 3
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- OPTASPLRGRRNAP-UHFFFAOYSA-N cytosine Chemical compound NC=1C=CNC(=O)N=1 OPTASPLRGRRNAP-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- RWQNBRDOKXIBIV-UHFFFAOYSA-N thymine Chemical compound CC1=CNC(=O)NC1=O RWQNBRDOKXIBIV-UHFFFAOYSA-N 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ASSKVPFEZFQQNQ-UHFFFAOYSA-N 2-benzoxazolinone Chemical compound C1=CC=C2OC(O)=NC2=C1 ASSKVPFEZFQQNQ-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- 229930024421 Adenine Natural products 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910014472 Ca—O Inorganic materials 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 241001455273 Tetrapoda Species 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229940104302 cytosine Drugs 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XVDBWWRIXBMVJV-UHFFFAOYSA-N n-[bis(dimethylamino)phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)N(C)C XVDBWWRIXBMVJV-UHFFFAOYSA-N 0.000 description 1
- WBIAWXNTQCZGMO-UHFFFAOYSA-N n-phenylthiatriazol-5-amine Chemical compound C=1C=CC=CC=1NC1=NN=NS1 WBIAWXNTQCZGMO-UHFFFAOYSA-N 0.000 description 1
- 239000002773 nucleotide Substances 0.000 description 1
- 125000003729 nucleotide group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GBECUEIQVRDUKB-UHFFFAOYSA-M thallium monochloride Chemical compound [Tl]Cl GBECUEIQVRDUKB-UHFFFAOYSA-M 0.000 description 1
- 229940113082 thymine Drugs 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 239000010981 turquoise Substances 0.000 description 1
- 229940035893 uracil Drugs 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
- C07F19/005—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00 without metal-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
- C07F15/0093—Platinum compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
Multi- or mixed-metal coordination complexes of a first metal M and a second metal M<1>, are obtained by reacting a solid salt of the metal M<1>, e.g. fluoride, chloride, nitrate etc. under anhydrous conditions with a solution of an anhydrous coordination complex of the metal M in a hydrocarbon solvent, that coordination complex being of the Formula RxM.nL, where R is an organic group which is the residue of an organic compound RH, where H represents a labile hydrogen atom replaceable by the metal M, x is the valency of the metal cation M, L is an organic donor ligand (Lewis base) and n is a whole number representing the number of ligand molecules in the complex. In that reaction, cations of the metal M<1> are captured by and enter into the crystallographic structure of the complex RxM.nL to form a multi- or mixed-metal coordination complex of the formula RxM.nLM<1>aZb, where R x M n and L are as defined above, M<1> is the second metal cation (which may be the same as or different from the metal cation M), b is the valency of the metal cation M<1>, Z is the anion of said metal salt, e.g. fluorine, chlorine, nitrate etc., and a is the valency of that anion.
Description
COMPLEXES OP METALLATED ORGANIC MOLECULES
COMPRISING MULTIPLE OR MIXED METALLIC SPECIES
This invention relates to complexes of metallated organic molecules comprising multiple and preferably mixed metallic species.
As used herein the term "multiple metallic species" refers to complexes containing at least two metal atoms forming coordination centres in the molecular structure of the complex, those two or more atoms not necessarily being different metallic species. "Mixed metallic species" on the other hand does specifically imply two or more different metal atoms each forming a coordination centre within one and the same complex.
Metallated complexes, i.e. complexes of a metal salt and an aprotic donor ligand such as hexamethylphosphoramide (HMPA), tetramethylenediamine (TMEDA), pentamethyldiethylenetriamine (PMDETA) and other aprotic Lewis bases, are of potential interest in a variety of different applications e.g. as a hydrocarbon or oil-soluble source of a reactive metal M, or as volatile sources of a metal M for metaloxide chemical vapour deposition (MO-CVD) applications.
In our recently filed U.K. Patent Application GB 9106834.6, we have disclosed a method for the preparation of metallated complexes containing not only an aprotic Lewis base donor ligand, but also a small protic Lewis base ligand, such as HZ0, NH3, H2S, HZSe or CH30H, coordinating the metal cation.
These metallated complexes are prepared by reacting a solid compound of a metal M and the protic Lewis base ligand, that is to say an oxide or hydroxide of the metal M, or an amide, hydroselenide or methoxide, with an organic compound RH containing two eiectronegative centres in the organic group R and either immediately adjacent each other or separated by a small linking or bridging group or atom, one such centre providing an "active" hydrogen atom which is replaceable by the metal M, the reaction being carried out under substantially anhydrous conditions in an aromatic hydrocarbon solvent, preferably toluene, containing the aprotic Lewis base donor ligand L. The reaction takes place readily at room temperature, or with gentle heating of the reaction mixture upto the boiling point of the aromatic solvent.
The product complex, usually in a well defined crystalline form, is recovered upon cooling of the reaction solution, e.g. by refrigeration.
The reaction, in the case of the metal hydroxide reactants, may be represented by the equation:
(aquo-complex)
Where M is the metal;
x is the valency of the metal M;
RH is an organic compound of the type Y-(R)-XH, where X and Y are both electronegative centres independently containing or consisting of N, O or S, and Rl is i) an aliphatic, aromatic or heterocyclic ring system, ii) a hydrocarbon or other aliphatic chain system, or (iii) a carbon atom attached to i) or ii) above or to hydrogen;
L is the aprotic Lewis base donor ligand;
n is the number of donor ligand molecules L, usually 1, 2, 3 or 4.
Similar equations and formulae may be written in the case of the amide, hydrosulphide, hydroselenide and methoxide reactants, save that in the formula of the product complex, the H20 ligand molecule is replaced by NH (ammino complexes) H2S (hydrosulphide complexes), H2Se (hydroselenide -complexes) or CHOH (methanol complexes), viz: RlM.nL.xNH3 (ammino) R,M. nL. xH,S (hydrosulphide) RxM.nL.xH2Se (hydroselenide)
and RxM.nL.xCH30H (methanol).
The characteristic feature of those complexes, and the organic compounds RH used to prepare them, is that, in the organic compound RH, the hydrogen atom replaceable by the metal M is attached to a first electronegative centre X, e.g. O, S, or NH linked either directly or by a small bridging or linking group in the group Rl to a second electronegative centre Y provided by either a carbonyl oxygen atom, i.e. a > C = 0 group, a thione sulphur atom, i.e. a > C = S group, or an imide nitrogen atom, i.e. a = NH group. This group provides, in effect, a flexible electronegative side arm which, in the molecular structure of the compound RxM.nL, is attracted towards and forms a donor bond with the adjacent cation of the metal M.However, in the course of forming a complex with an inorganic protic Lewis base ligand molecule, i.e. a H20 ligand molecule in the case of the aquo complexes, a NH molecule in the case of the ammino complexes, an H2S or H2Se molecule in the case of the hydrosulphido and hydroseleno complexes respectively, or a CHOH molecule in the case of the methanol complexes, that bond is broken by the incoming protic Lewis base ligand molecule which then forms a hydrogen bond with the now displaced electronegative centre, i.e. the carbonyl oxygen atom, the thione sulphur atom or the imide nitrogen atom, as the case may be, and a new donor ligand bond with the metal cation.In effect, the "flexible" electronegative side arm "swings" away from metal cation to admit the incoming protic donor ligand, the molecular structure of the final complex thus showing a much increased interatomic spacing between the metal cation and the electronegative centre Y.
In the case of a typical aquo complex, and a typical heterocyclic organic acid 2-ercaptobenzoxazole, the structure of the complex may be represented as:
Where M represents the metal;
L represents the aprotic Lewis base donor ligand; n is the number of ligand molecules L, usually 1 or 2; ------ represents a hydrogen bond; and
represents a donor ligand bond.
A further characteristic of those aquo complexes is that, upon heating, they convert readily back into the anhydrous form, e.g.:
by loss of the H20 or other small protic donor ligand molecule - i.e.
NH3, H2S, H2Se or MeOH. That loss is accompanied by a reduction in the interatomic distance between the metal cation and the electronegative centre Y, i.e. in the case shown, the adjacent thione sulphur atom ( > C = S).
The preparation of anhydrous complexes of that type, e.g. the complex
has previously been described in J.Chem. Soc., Chem. Commun., 1990, Issue No. 8 p 643, com. 0/00262C.
In that case the anhydrous complex, which can be converted to the aquo complex by the addition of the stoichiometric quantity of water, is prepared by reacting a suitable source of the metal M, i.e. the metal itself, a metal hydride or metal alkyl, with the organic compound containing an "active" hydrogen atom replaceable by the metal M, such reaction being carried out in an aromatic hydrocarbon solvent, preferably toluene, and in the presence of the aprotic donor ligand or
Lewis base L.
For example, the anhydrous lithiated complex referred to is prepared by the reaction of n-butyl lithium with 2-mercaptobenzoxazole in a solution of TMEDA in toluene, i.e. the reaction:
Because the conversion of that anhydrous complex into the corresponding aquo complex requires the closely controlled addition of the precise stoichimetric quantity of water (obtainable only under precise laboratory or experimental conditions) the direct route described in GB 9106834.6, i.e. the reaction of the organic compound containing the replaceable hydrogen atom with a solid metal oxide or hydroxide under anhydrous conditions in toluene, is much to be preferred.Similarly, that latter route has advantages in the preparation of the anhydrous complexes, in view of a) the readily available starting materials, i.e. oxides and hydroxides, and b) the ready dehydration of the aquo complexes by heating in vacuo.
The present invention is based on the discovery that those anhydrous complexes, i.e. coordination complexes of a) a compound formed from a metal M, preferably an alkali or alkaline earth metal such as Ca, Ba, or Sr, and an organic compound RH having an active hydrogen on a first electronegative centre and adjacent or near to a second electronegative centre in the organic group R, and replaceable by the metal M, and b) an aprotic donor ligand or Lewis base L coordinating the metal atom or atoms M, have the ability to form multiple or mixed metal complexes by the capture of a metal salt of the formula 1 where Mi is a metal cation, which may be the same as, but is preferably different from the metal M, Z is an anion, preferably halide, e.g. F, C1-, B & or I-, or NQ, , SO42, CO2, etc., a is the valency of the anion X and b is the valency of the cation ML.
In the course of the "capture" of the metal salt MlaZb by the complex RxM.nL (where R is the organic residue of the organic compound
RH following the displacement of the "active" hydrogen by the metal M,
L represents the aprotic donor ligand or Lewis base coordinating the metal M and n is the number of ligand molecules present in the complex and x is the valency of the metal M), it is found that the interatomic spacing between the metal atom M and the second electronegative centre in the group R increases to admit the incoming cation of the second metal Mt, which, in the multi-or mixed metal complex, forms a coordination centre for the electronegative centres in the R groups attached to the first metal M, with consequent displacement from the incoming salt of the anions Z.
Thus, generalising the formula hereinbefore given for the anhydrous complex to:
where M, L and n are as hereinbefore defined;
Y is O, S or NH;
X is O, S, NH or -CH; and
R is an organic residue optionally forming a cyclic
structure with X, the general formula of the product complex following the capture of the salt MlaZb may be represented by the formula:
where Mt represents the incoming metal cation, which may be the same as, but which will preferably be different from the first metal cation M, and which, in the product complex, becomes coordinated by the electronegative centres Y, whilst the incoming anions Z are displaced from the metal Ml onto the metal M.
The capture of the metal salt MlaZb by the anhydrous complex RxM.nL takes place readily upon dissolving the metal salt MlaZb in a solution of the anhydrous complex in an aromatic solvent, preferably toluene. Dissolving the metal salt in the anhydrous complex solution is assisted by heating and/or by agitation or stirring. The multi-or mixed metal coordination complex is recoverable, usually in a well defined crystalline form, by cooling the reaction mixture, e.g. by refrigeration, and following which the product complex can be purified, as necessary, by well established recrystallisation procedures.
The invention is illustrated by the following Example and accompanying drawings describing the preparation of a novel mixed metal coordination complex according to the present invention and illustrating the resulting molecular structures: Fig. 1 illustrating the molecular structure of the resulting complex cation, and Fig. 2 illustrating the molecular structure of the complex anion.
Example
Synthesis and structure of the mixed metal-coordination complex (Ox2Ca.2HMPA)2.Pt Cl.(CaCl2.2HMPA). (toluene)2 Where "Ox" is the 2-mercaptobenzoxazolyl anion
Preparation of the anhydrous complex Ox2Ca.2HMPA
The anhydrous complex Ox2Ca.2HMPA was prepared by the method of
Example 2 of GB 9106834.6, that is to say by reacting substantially anhydrous solid calcium hydroxide with 2-mercaptobenzoxazole in solution in toluene in the presence of HMPA (HMPA = hexamethyl phosphoramide O:P(NMe2)3), following which the aquo complex, Ox2Ca.2HMPA.2H2O, was recovered in crystalline form, mp. 104-1060C.
Heating the aquo complex in vacuo at 130C for two hours provides
(aquo complex) (anhyd. complex) Reaction of anhydrous complex Ox2Ca.2HMPA with PtCl2
Platinum (II) chloride (0.266g, 1 mmol) was added to a solution of the anhydrous complex Ox2Ca.2HMPA (1.050g, 1.5 mmol) in 10 mL toluene. The mixture was heated to 1000C for 15 minutes by which time all the solid PtCl2 had reacted leaving a bright yellow solution and a small quantity of yellow powder, later determined to be Ox2Pt.
Filtration and cooling of the filtrate to 200C produced yellow cubic crystals of (Ox2Ca.2HMPA)2PtCl2.(CaCl2.2HMPA). 2 (toluene), first batch yield 0.66g 56%; m.p. 210-2130C; elemental analysis: found C 40.0, H 6.0, Cl 6.4, N 13.2, P 7.7%; calculated: C 40.4, H 6.0, Cl 6.1,
N 13.3, P 8.0%; 1H NMR [(CD3)2SO, 250 MHz, 200C] 6 centred ca.7.1 (m,26H of four Ox anions and aromatic protons of two solvating toluene molecules), 2.53 (d,108H of six HMPA ligands, J 9.5Hz), 2.30 (s,6H, methyl protons of two solvating toluene molecules).
The solid state structure of the product complex, determined by
X-ray crystallography, shows that it consists of a dinuclear calcium chloride-complexed cation, [(HMPA)3Ca. (ll2-Cl)3.Ca(HMPA)3]t, and a mixedmetal anion, [Pt(Ox)4.CaCl]; in addition, there are two toluene solvate molecules which lie in general positions in the lattice and do not interact strongly with either the cation or the anion. The cation (Figure 1) consists of two pseudo-octahedral Ca2t ions linked by three -C1 ions [mean Ca-Cl distance, 2.80(1)A] and complexed terminally by three HMPA ligands each [mean Ca-O distance, 2.27(2).
The structure of the anion is shown in Figure 2. Here a pt2 centre is coordinated by the four C. .. side-arms of four Ox groups [mean Pt-S distance, 2.32(2)A] to give a square planar coordination geometry (Pt deviates by 0.1 from the Sfl plane); such a square planar arrangement is the norm for Pt (II) complexes. The 2-N centres of these Ox anions in turn bind to a Ca2t centre [mean Ca-N distance, 2.46(2)] which lies directly above the Pt [Ca...Pt distance, 2.960(5)A]. Finally, a capping C renders the Ca2t centre square-based pyramidal. Overall, the anion structure can be viewed as a tetrapod OxsCaCl3 ligand coordinated to a Put2? cation.
By following the same general techniques, mixed-metal complexes have been prepared from the following reaction pairs:
Metal Chelate Metal Salt Product
(R,M.nL) (M'aZb) (RIM-nL-M aZb) Ox2Ca.2HMPA PdCl2 Orange crystals
NiCl2 Yellow crystals CoCl2 Turquoise crystals " SnCl2 White powder
PbBr2 Yellow powder OxzBa.3HMPA PdCl2 Orange crystals l(OxO)Ca.2HMPA TiCl3 Orange crystals
2(AntS)2Sr.3HMPA PtC12 Yellow crystals TlCl Brown solution
OxOH = 2-hydroxybenzoxazole
2 AntSH = 5-anilino - 1, 2, 3, 4 - thiatriazole
The overall reaction of the anhydrous complex Ox2Ca.2HPMA with the PtCl2 may thus be viewed as a "capture" of the PtC12 by the complex, with the ptZt cation displacing the side arm bonds between two Ca2t cations and the nearby sulphur atoms of their respective Ox anions in two molecules of the anhydrous complex, the incoming pt2t cation thus becoming a coordination centre for four coordinating sulphur atoms of four Ox anions, the ss-N centres of which remain bound to one Ca centre of the cation. As a result of that capture, also, the two anions of
PtClZ are displaced, with one ending up in the dicalcium cation, and the other ending up in the mixed metal anion.
The above results are believed to be of considerable significance in showing the ability of anhydrous "side-arm" donating complexes of the type described, i.e. Lewis base donor ligand coordinated complexes of metal containing compounds of the type RM where M is a metal atom replacing an active hydrogen of an organic compound RH in which the hydrogen atom replaceable by the metal M lies close to an electronegative centre Y in the group R, to act as ligand to other metals, thus giving rise to mixed-metal complexes of the type described. Indeed it has already been shown that anhydrous complexes of the type described will dissolve salts of other metals besides platinum, e.g. PdCl2, CoCl2, NiCl2 and SnCl2 to give well defined crystalline products.
In the anhydrous complex, a wide variety of metal cations may be used: alkali metal cations, alkaline earth metal cations, rare earth and transition metal cations. It is also possible that the process of the invention will be applicable to the manufacture of mixed of alkaline earth metal complexes, i.e. containing two different alkaline earth metals, e.g. combinations of Ca/Ba, Ba/Sr, Ca/Sr, etc, and which may be of utility in mixed metal MO-CVD applications.
Likewise, the anhydrous complexes may be used to capture a wide range of metal salts, with particular interest centering on the capture of alkaline earth metal salts, as already indicated, to give rise to mixed alkaline earth metal complexes, on the noble metal salts, e.g.
Pt, Pd, etc., giving rise to mixed alkali metal/noble metal complexes and to mixed alkaline earth/noble metal complexes, and on the capture of transition metals to form mixed alkali or alkaline earth/transition metal complexes.
The organic compounds RH used to prepare the anhydrous complexes and containing an "active" hydrogen on a first electronegative centre
X and close to a second electronegative centre Y in R and replaceable by the first metal M, may be any of a wide variety of organic compounds containing such an "active" hydrogen atom. Of especial interest are
B-diketones, especially fluorinated diketones, i.e. compounds of the formula RFC(O)CH2C(O)Rg where R? is perfluoroalkyl, and heterocyclic compounds of the 2-mercaptobenzoxazole type, comprising a
group forming part of a heterocycle, Y being selected from 0, S and NH, especially 0 or S. Typical compounds of this type are listed in GB 9106834.6 and include, besides 2-mercaptobenzoxazole, succinimide, 2mercaptopyrimidine, 2-mercaptothiazoline, 2-mercaptobenzimidazole, 2 oxobenzazole and the nucleotide "bases" cytosine, thymine, uracil, guanine and adenine.
As the aprotic donor ligand or Lewis base, hereinbefore mentioned, i.e. HMPA, TMEDA, PMDETA, etc, numerous other. such donor ligands will be apparent to the person skilled in the art and will include - inter alia: N.N-dimethylpropylidene urea (DMPU), diethyl ether, 1,2-dimethyloxyethane (glyme), bis(2-methoxymethyl) ether (diglyme), dioxan, tetrahydrofuran and dimethylimidazole (DMI) etc.
Claims (15)
1. A multi-or mixed metal coordination complex of a first metal M, and containing a second metal Mt, which may be the same as or different from the metal M, and obtainable by reacting a solid salt of the metal M under substantially anhydrous conditions with a solution of a substantially anhydrous coordination complex of the first metal M in an aromatic hydrocarbon solvent, the said substantially anhydrous coordination complex being of the formula R,M.nL, where R is the residue of an organic compound, containing an active hydrogen replaceable by the metal M and located on a first electronegative centre adjacent or near to a second electronegative atom in the organic group R, L is an aprotic donor ligand or Lewis base, n is a number indicating the number of ligand molecules in the complex and x is the valency of the metal M, the multi-or mixed metal coordination complex being representable by the formula RxM.nL.MlaZb, where M and Ml and the first and second metals, respectively, R, n, x, and L are as above defined, Z is an anion, a is the valency of the anion Z and b is the valency of the metal Ml.
2. A coordination complex according to claim, wherein M and M1 are different.
3. A coordination complex according to claim 1 or 2, wherein M is an alkali metal an alkaline earth metal, a noble metal or a transition metal.
4. A coordination complex according to claim 1, 2, or 3, wherein is an alkali metal, an alkaline earth metal, a noble metal or a transition metal in general.
5. The complex (OxZCa.2HMPA)2.PtCl.(CaClg.2HMPA) (toluene) where Ox = 2-mercaptobenzoxazolyl and HMPA represents hexamethylphosphoramide.
6. A method for the preparation of multi-or mixed metal coordination complexes of a first metal M, containing a second metal Ml, which may be the same as or different from the metal M, which comprises reacting, under substantially anhydrous conditions, a solution of a substantially anyhdrous coordination complex of the first metal M in an aromatic hydrocarbon solvent, the said substantially anhydrous coordination complex being of the formula Rt.M.nL, where R is the residue of an organic compound containing an active hydrogen replaceable by the metal
M and located on a first electronegative centre adjacent or near to a second electronegative atom in the organic group R, L is an aprotic donor ligand or Lewis base, n is a number indicating the number of ligand molecules in the complex and x is the valency of the metal M, with a solid salt of the metal M and representable by the formula MlaZb where Z is an anion of valency a and b is the valency of the metal cation Mt thereby to produce a multi-or mixed-metal coordination complex of the formula RxM.nL.MlaZb where M, M1, R, L, Z, a, b, n and x are as above defined.
7. A method according to claim 6, wherein M is an alkali metal, an alkaline earth metal, a noble meta] or a transition metal.
8. A method according to claim 6 or 7 wherein Ml is an alkali metal, an alkaline earth metal, a noble metal or a transition metal.
9. A method according to claim 6, wherein M is an alkali metal, an alkaline earth metal, a noble metal or a transition metal, and M1 is an alkali metal, alkaline earth metal, a noble metal or a transition metal, M and M1 being different.
10. A method according to claim 9, wherein M is an alkali metal and
M1 is an alkaline earth metal, or M is an alkali metal or alkaline earth metal and M1 is a noble metal or a transition metal.
11. A method according to any one of claims 6 - 8, where Z in the formula of the metal salt is F, C1, Br, I, NQ , soll or CQ2
12. A method according to any one of claims 6 to 12, where R in the formula of the anhydrous coordination complex is derived from a 13diketone or a heterocyclic organic compound containing a
group as part of the heterocyclic ring where Y is O, S or NH.
13. A method according to claim 12, where R is 2mercaptobenzoxazolyl, 2-mercaptopyrimidyl, 2-mercaptothiazolyl, 2mercaptobenzimidazolyl or 2-oxobenzazolyl.
14. A method according to any one of claims 6 to 11, where L in the formula of the anhydrous coordination complex is HMPA, TMEDA, PMDETA,
DMPU, DMI, diethylether, 1,2-methyloxyethane, bis(2-methoxymethyl) ether, dioxan or tetrahydrofuran.
15. A method according to any one of claims 6 to 14, wherein the hydrocarbon solvent for the reaction is toluene.
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