CN111423470A - 一种磷杂苯钼的π络合物及其制备方法与应用 - Google Patents
一种磷杂苯钼的π络合物及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种磷杂苯钼的π络合物及其制备方法与应用，所述络合物的结构式为：
所述化合物的制备方法为磷杂苯化合物和六羰基钼在甲苯中进行回流反应得到红色固体的络合物。该络合物在同一个环上既有η1配位又有η6配位，能够作为催化剂用于多种金属催化反应；该络合物具有稳定性强、催化效率高的优点，能够应用于钼催化CO插羰反应中；该络合物的制备方法具有合成步骤短、合成产率高、后处理简单和合成的产物稳定的优点。
Description
技术领域
本发明涉及有机合成领域，具体涉及一种磷杂苯钼的π络合物及其制备方法与应用。
背景技术
磷杂苯化合物具有特殊的电子属性，磷杂苯可以通过磷原子上的孤对电子和金属形成配合物，得到磷杂苯金属络合物。磷杂苯通常被用来作为催化剂配体参与金属催化的有机合成反应，例如磷杂苯作为π受体在参与铑催化的烯烃的甲醛化方面有广泛的应用报道(Catal.Sci.Technol.,2014,4,979-987)。
钼是过渡态金属元素，其符号为Mo，属于铬族元素。钼金属外表呈银白色，在自然界多以混合态形式存在，例如辉钼矿(MoS)和五矿(PbMoO)。钼通常作为催化剂用于工业生产，以钼为主要活性组分的加氢精制催化剂在工业上的应用以有40多年的历史，具有优越的抗硫新能和高效的催化活性。以钼为金属元素制备的磷杂苯类金属配合物在金属催化反应邻域具有优异的催化效果。
Peter A等人制备的η6磷杂苯络合物是用预先制备好的[Mo(CO)3(MeCN)3]与磷杂苯在甲苯里室温搅拌后在金属钯的催化下制备得到如下的双η1-η6络合物(Organometallics,2019,38,1595-1605)：
发明内容
本发明旨在至少解决现有技术中存在的技术问题之一。为此，本发明提出一种磷杂苯钼的π络合物，能够提供一种新的双η1-η6磷杂苯钼络合物，该络合物的制备工艺简单。
本发明还提出上述络合物的制备方法。
本发明还提出上述络合物的应用。
根据本发明的第一方面实施例的络合物，所述络合物的结构式如下：
根据本发明第一方面实施例的络合物，至少具有如下有益效果：该络合物是一种新的双η1-η6络合物，在同一个环上既有η1配位又有η6配位，能够作为催化剂用于多种金属催化反应；该络合物的优点在于：1)稳定性大幅提高，由于磷杂苯里面的磷元素被Mo(CO)5保护，不容易被氧化，增强了稳定性；2)磷杂苯作为π受体配体，由于更大的位阻，在催化时利于还原消除，从而提高了催化效率。
根据本发明的第二方面实施例的制备方法，包括以下步骤：磷杂苯化合物和六羰基钼进行回流反应得到所述络合物；所述磷杂苯化合物结构式如下：
根据本发明第二方面实施例的制备方法，至少具有如下有益效果：该方法合成步骤短，只需一步反应即可合成目标化合物；该方法的合成产率高、后处理方法简单且合成的产物稳定；因此，该方法具有高效和易操作等优点。
根据本发明的一些实施例，反应溶剂为甲苯。
根据本发明的一些实施例，磷杂苯化合物与六羰基钼的摩尔比为1：(2～3)。
作为优选的，磷杂苯化合物与六羰基钼的摩尔比为1：2.5。
根据本发明的一些实施例，反应温度为(110～120)℃。
根据本发明的一些实施例，反应时间为(3～8)h。
根据本发明的一些实施例，所述制备方法还包括分离纯化操作，所述分离纯化包括以下步骤：在(-10～-4)℃温度下使用梯度溶剂通过硅胶柱进行纯化。
作为优选的，所述梯度溶剂为二氯甲烷/正己烷从1：5到1:1。
根据本发明的第三方面实施例的应用，上述络合物能够用于金属催化CO插羰反应中。
根据本发明的一些实施例，所述金属催化CO插羰反应包括催化CO和CH3OH合成醋酸甲酯和醋酸的反应。
根据本发明第三方面实施例的制备方法，至少具有如下有益效果：所述络合物结构新颖，在金属催化反应中具有广泛的应用前景。
本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。
附图说明
图1为本发明实施例中络合物的X-ray晶体结构图。
具体实施方式
为详细说明本发明的技术内容、所实现目的及效果，以下结合实施方式并配合附图予以说明。
实施例：
1、磷杂苯钼的π络合物的制备
在氮气保护下，向甲苯(6mL)中加入磷杂苯化合物1(273mg，1.0mmol)和六羰基钼(660mg，2.5mmol)并回流4小时。然后，将混合物冷却至室温，并使用梯度溶剂(二氯甲烷/正己烷＝1：5～1：1)在-6℃情况下在硅胶柱上直接纯化，得到目标络合物3(576mg，82％产率)，产物为红色固体。目标络合物3的磷谱、氢谱、碳谱的核磁数据以及质谱数据如下所示：
31P NMR:(CDCl3):δ74.09(3JPH＝8.8Hz)；1H NMR(CDCl3):δ1.32(t,3JHH＝7.0Hz,3H,CH3),2.02(s,3H,CH3),2.49(s,3H,CH3),4.4122-4.38(m,2H,CH2),6.82(d,3JPH＝11.0Hz,1H,CH),6.90(d,JPH＝6.4Hz,1H,CH),7.32-7.41(m,4H,CH)；13C NMR(CDCl3):δ14.14(s,＝CH3),19.43(s,＝CH3),21.69(s,＝CH3),62.32(s,＝CH2),88.24(d,1JCP＝20.1Hz,＝C),98.36(d,JCP＝5.8Hz,＝C),104.72(d,3JCP＝15.7Hz,＝CH),117.69(d,2JCP＝18.2Hz,＝C),128.78(d,JCP＝20.1Hz,＝CH),129.5s,＝CH),131.91(d,JCP＝4.8Hz,＝CH),135.29(d,JCP＝4.8Hz,＝CH),136.40(d,1JCP＝17.2Hz,＝C),166.05(d,2JCP＝7.3Hz,CO),203.33(d 2JCP＝11.5Hz,cis-CO),210.21(d 2JCP＝39.3Hz,trans-CO),215.84(s,＝CO)；HRMS m/z690.8600(calcd for C24H17Mo2O10P-H,690.8595)。
在90℃条件下，甲苯中的六羰基钼与磷杂苯反应速度快、清洁且收率好，可以通过控制起始物比例得到不同的络合物2或者3。如果加入1：1的磷杂苯和Mo(CO)6只得到中间体配合物2。如果加入过量的Mo(CO)6，中间体配合物2能够继续与过量的六羰基钼继续发生反应生成η6络合物3，X-ray单晶衍射证明了络合物3的结构。
2、磷杂苯钼的π络合物的晶体结构
图1是实施例1制备的双η3-η6的络合物的X-ray单晶衍射图。其中，主键长
和键角(deg)分别为：P1-Mo1 2.480(4),P1-C12 1.769(14),P1-C18 1.770(15),P1-Mo2 2.537(4),C12-C13 1.438(19),C13-C14 1.411(19),C14-C16 1.440(19),C16-C18 1.41(2),Mo1-C52.005(16),Mo2-C12 2.341(14),Mo2-C13 2.331(16),Mo2-C14 2.409(14),Mo2-C162.371(14),Mo2-C18 2.382(13)C12-P1-C18 100.7(7)。
η6络合物3最显著的特征是1H NMR和13C NMR光谱中向高场偏移。此外，Mo上的3个羰基因为快速旋转在13C NMR频谱上显示为一个单峰，磷谱31P在δ215.84ppm。之后，尝试通过加热用DPPE来去除σMo(CO)5并保留η6络合物，然而，在热条件下，π络合物比α络合物更容易分解。
3、原料磷杂苯化合物1的合成
磷杂苯化合物1通过以下合成路径合成：
4、磷杂苯钼的π络合物的应用
本实施例制备的磷杂苯钼的π络合物能够作为催化剂应用于钼催化CO插羰酯化反应中，对催化CO和CH3OH合成醋酸甲酯和醋酸的反应有高效的催化效果。
综上所述，本发明提供了提供一种新的双η1-η6磷杂苯钼络合物，该络合物在同一个环上既有η1配位又有η6配位，能够作为催化剂用于多种金属催化反应；该络合物具有稳定性强、催化效率高的优点，能够应用于钼催化CO插羰酯化反应中；该络合物的制备方法具有合成步骤短、合成产率高、后处理简单和合成的产物稳定的优点。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等同变换，或直接或间接运用在相关的技术领域，均同理包括在本发明的专利保护范围内。
Claims (10)
1.一种磷杂苯钼的π络合物，其特征在于，所述络合物的结构式如下：
2.权利要求1所述的磷杂苯钼的π络合物的制备方法，其特征在于，包括以下步骤：磷杂苯化合物和六羰基钼进行回流反应得到所述络合物；所述磷杂苯化合物结构式如下：
3.如权利要求2所述的制备方法，其特征在于，反应溶剂为苯类溶剂；作为优选的，所述反应溶剂为甲苯和二甲苯中的至少一种。
4.如权利要求2所述的制备方法，其特征在于，磷杂苯化合物与六羰基钼的摩尔比为1：(2～3)。
5.如权利要求4所述的制备方法，其特征在于，磷杂苯化合物与六羰基钼的摩尔比为1：2.5。
6.如权利要求2所述的制备方法，其特征在于，反应温度为(110～120)℃。
7.如权利要求2所述的制备方法，其特征在于，反应时间为(3～8)h。
8.如权利要求2所述的制备方法，其特征在于，所述制备方法还包括分离纯化操作，所述分离纯化包括以下步骤：在(-10～-4)℃温度下使用梯度溶剂通过硅胶柱进行纯化；所述梯度溶剂为二氯甲烷：正己烷从1:5到1:1。
9.权利要求1所述的磷杂苯钼的π络合物在金属催化CO插羰反应中的应用。
10.如权利要求9所述的应用，所述金属催化CO插羰反应包括催化CO和CH3OH合成醋酸甲酯和醋酸的反应。
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