两性离子配体EtNHC(S)Ph2P═NPPh2C(S)NEt与[Ru3(CO)12]的反应活性。硫转移和配体碎片化导致亚甲基酰胺[-N(Et)-CH(R)-]μ3-桥连部分的形成。

Reactivity of the zwitterionic ligand EtNHC(S)Ph2P[double bond, length as m-dash]NPPh2C(S)NEt towards [Ru3(CO)12]. Sulfur transfer and ligand fragmentation leading to the methideylamide [-N(Et)-CH(R)-] micro3-bridging moiety.

作者信息

Delferro Massimiliano, Pattacini Roberto, Cauzzi Daniele, Graiff Claudia, Terenghi Mattia, Predieri Giovanni, Tiripicchio Antonio

机构信息

Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Università di Parma, Via G.P. Usberti 17/A, 43100, Parma, Italy.

出版信息

Dalton Trans. 2009 Jan 21(3):544-9. doi: 10.1039/b812050a. Epub 2008 Nov 12.

DOI:10.1039/b812050a

PMID:19122912

Abstract

The reaction of EtNHC(S)Ph2P[double bond, length as m-dash]NP+Ph2C(S)N(-)Et (HEtSNS) with [Ru3(CO)12] has been carried out under two different experimental conditions: in the first case [Ru3(CO)12], previously turned into the labile intermediate [Ru3(CO)10(CH3CN)2], afforded, at room temperature in dichloromethane, the trinuclear clusters [Ru3(CO)11(CNEt)] (1), [Ru3(CO)9(micro-H)[(micro-S:kappa-P)Ph2PN[double bond, length as m-dash]PPh2C(S)NEt]] (2), [Ru3(CO)9(micro-H)[(micro-S:kappa-P)Ph2PN[double bond, length as m-dash]P(S)Ph2]] (3) and [Ru3(CO)10[(micro-kappa2P)Ph2PNHPPh2]] (3). Ligand fragmentation occurs via loss of EtNC or EtNCS, without sulfur transfer to the cluster core. In the second case, [Ru3(CO)12] reacted with HEtSNS in toluene at 70 degrees C, giving the trinuclear clusters , [Ru3(CO)7(CNEt)(micro3-S)[(micro2-N:eta1-C:kappa1-P)Ph2PN[double bond, length as m-dash]PPh2C(H)NEt]] (6), [Ru3(CO)8)(micro3-S)[(micro2-N:eta-C:kappa-P)Ph2PN[double bond, length as m-dash]PPh2C(H)NEt]] (6) and [Ru3(CO)6(micro3-CO)(micro3-S)(EtNC)[(micro-kappa2P) Ph2PNHPPh2]] (7). The last three compounds derive from ligand fragmentation and sulfur transfer to the metal cluster. All compounds were characterized by spectroscopy (NMR, IR) and the molecular structures of , and were determined by single-crystal X-ray diffraction. Cluster preserves the original Ru3 triangular core in which an edge is bridged by a hydride ligand and by the sulfur atom of the Ph2PN[double bond, length as m-dash]PPh2C(S)NEt ligand. Cluster shows an open triangle of Ru atoms capped by a micro3-sulfide and by the unprecedented methideylamide -N(Et)CH(R)-micro3-bridging moiety of the Ph2PN[double bond, length as m-dash]PPh2C(H)NEt ligand. It formally derives from cluster by substitution of ethyl isonitrile with one CO molecule. Finally, cluster displays a Ru3(micro3-S)(micro3-CO) trigonal bipyramidal core.

摘要

在两种不同的实验条件下，使EtNHC(S)Ph2P═NP⁺Ph2C(S)N⁻Et（HEtSNS）与[Ru3(CO)12]发生反应：在第一种情况下，预先转化为不稳定中间体[Ru3(CO)10(CH3CN)2]的[Ru3(CO)12]，于室温下在二氯甲烷中反应，得到三核簇合物[Ru3(CO)11(CNEt)]（1）、[Ru3(CO)9(μ-H)[(μ-S:κ-P)Ph2PN═PPh2C(S)NEt]]（2）、[Ru3(CO)9(μ-H)[(μ-S:κ-P)Ph2PN═P(S)Ph2]]（3）和[Ru3(CO)10[(μ-κ2P)Ph2PNHPPh2]]（3）。配体断裂通过EtNC或EtNCS的损失发生，没有硫转移到簇核。在第二种情况下，[Ru3(CO)12]与HEtSNS在70℃的甲苯中反应，得到三核簇合物[Ru3(CO)7(CNEt)(μ3-S)[(μ2-N:η1-C:κ1-P)Ph2PN═PPh2C(H)NEt]]（6）、[Ru3(CO)8)(μ3-S)[(μ2-N:η-C:κ-P)Ph2PN═PPh2C(H)NEt]]（6）和[Ru3(CO)6(μ3-CO)(μ3-S)(EtNC)[(μ-κ2P) Ph2PNHPPh2]]（7）。后三种化合物源自配体断裂和硫转移到金属簇。所有化合物均通过光谱（NMR、IR）进行表征，并且通过单晶X射线衍射确定了（此处原文缺失具体化合物编号）、（此处原文缺失具体化合物编号）和（此处原文缺失具体化合物编号）的分子结构。簇合物（此处原文缺失具体化合物编号）保留了原始的Ru3三角形核心，其中一条边由一个氢化物配体和Ph2PN═PPh2C(S)NEt配体的硫原子桥连。簇合物（此处原文缺失具体化合物编号）显示出由一个μ3-硫化物和Ph2PN═PPh2C(H)NEt配体前所未有的甲酰亚胺基 -N(Et)CH(R)-μ3-桥连部分封端的Ru原子开放三角形。它正式地通过用一个CO分子取代乙基异腈从簇合物（此处原文缺失具体化合物编号）衍生而来。最后，簇合物（此处原文缺失具体化合物编号）展示出一个Ru3(μ3-S)(μ3-CO)三角双锥核心。