氢化有机金属碳链：丁二炔基（CH[双键，长度为破折号]CHC[三键，长度为破折号]C）作为缺失的一环。

Hydrogenating an organometallic carbon chain: buten-yn-diyl (CH[double bond, length as m-dash]CHC[triple bond, length as m-dash]C) as a missing link.

机构信息

Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory ACT 2601, Australia.

出版信息

Dalton Trans. 2019 Nov 12;48(44):16534-16554. doi: 10.1039/c9dt03229k.

DOI:10.1039/c9dt03229k

PMID:31576871

Abstract

The sequential reaction of [Ru(C[triple bond, length as m-dash]CC[triple bond, length as m-dash]CH)Cl(CO)2(PPh3)2] with [Ru(CO)2(PPh3)3], and N-chlorosuccinimide affords the binuclear tetracarbido complex [Ru2(μ-C[triple bond, length as m-dash]CC[triple bond, length as m-dash]C)Cl2(CO)4(PPh3)4]. This may be compared with the first example of a butenyndiyl bridged bimetallic complex [Ru2(μ-CH[double bond, length as m-dash]CHC[triple bond, length as m-dash]C)Cl2(CO)4(PPh3)4] which is obtained from the reaction of [Ru(C[triple bond, length as m-dash]CC[triple bond, length as m-dash]CH)Cl(CO)2(PPh3)2] with [RuHCl(CO)(PPh3)3] followed by carbonylation. Characterisational data are discussed with reference to constituent model complexes [Ru(C[triple bond, length as m-dash]CH)Cl(CO)2(PPh3)2] and [Ru(CH[double bond, length as m-dash]CH2)Cl(CO)2(PPh3)2] in addition to DFT analysis of the bonding in the complexes [Ru2(μ-L)Cl2(CO)4(PMe3)4] (L = C[triple bond, length as m-dash]C-C[triple bond, length as m-dash]C, CH[double bond, length as m-dash]CHC[triple bond, length as m-dash]C, CH[double bond, length as m-dash]CH-CH[double bond, length as m-dash]CH). A range of other tetracarbido complexes which may be prepared from [RuCl(C[triple bond, length as m-dash]CC[triple bond, length as m-dash]CH)(CO)2(PPh3)2] is also described and includes [RuAu(μ-C4)Cl(CO)3(PPh3)3], [RuIr(μ-C4)Cl(CO)3(PPh3)4], [RuIr(μ-C4)H(NCMe)(CO)3(PPh3)4]BF4, [RuIr(μ-C4)Cl(η2-O2)(CO)3(PPh3)4], [Ru2Hg(μ-C4)2Cl2(CO)4(PPh3)4], [Ru2Pt(μ-C4)2Cl2(CO)4(PPh3)6] and [Ru2(μ-C4)HCl(CO)4(PPh3)4].

摘要

[Ru(C[三键,长度为破折号]CC[三键,长度为破折号]CH)Cl(CO)2(PPh3)2]与[Ru(CO)2(PPh3)3]的连续反应，以及 N-氯代丁二酰亚胺，得到双核四碳化物配合物[Ru2(μ-C[三键,长度为破折号]CC[三键,长度为破折号]C)Cl2(CO)4(PPh3)4]。这可以与第一个丁烯二基桥联双金属配合物[Ru2(μ-CH[双键,长度为破折号]CHC[三键,长度为破折号]C)Cl2(CO)4(PPh3)4]进行比较，后者是通过[Ru(C[三键,长度为破折号]CC[三键,长度为破折号]CH)Cl(CO)2(PPh3)2]与[RuHCl(CO)(PPh3)3]的反应得到的，然后进行羰基化反应。特征数据与组成模型配合物[Ru(C[三键,长度为破折号]CH)Cl(CO)2(PPh3)2]和[Ru(CH[双键,长度为破折号]CH2)Cl(CO)2(PPh3)2]一起进行了讨论，此外还对配合物[Ru2(μ-L)Cl2(CO)4(PMe3)4]（L = C[三键,长度为破折号]C-C[三键,长度为破折号]C、CH[双键,长度为破折号]CHC[三键,长度为破折号]C、CH[双键,长度为破折号]CH-CH[双键,长度为破折号]CH）中的键合进行了 DFT 分析。还描述了一系列其他可能由[RuCl(C[三键,长度为破折号]CC[三键,长度为破折号]CH)(CO)2(PPh3)2]制备的四碳化物配合物，包括[RuAu(μ-C4)Cl(CO)3(PPh3)3]、[RuIr(μ-C4)Cl(CO)3(PPh3)4]、[RuIr(μ-C4)H(NCMe)(CO)3(PPh3)4]BF4、[RuIr(μ-C4)Cl(η2-O2)(CO)3(PPh3)4]、[Ru2Hg(μ-C4)2Cl2(CO)4(PPh3)4]、[Ru2Pt(μ-C4)2Cl2(CO)4(PPh3)6]和[Ru2(μ-C4)HCl(CO)4(PPh3)4]。