Homo- and Heteropolynuclear Complexes Containing Bidentate Bridging 4-Phosphino-N-Heterocyclic Carbene Ligands

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• 作者：Zeyu Han ; Joshua I. Bates ; Dominik Strehl ; Brian O. Patrick ; Derek P. Gates
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：May 16, 2016
• 年：2016
• 卷：55
• 期：10
• 页码：5071-5078
• 全文大小：441K
• 年卷期：0
• ISSN：1520-510X

文摘

The abnormal reaction of phosphaalkenes with N-heterocyclic carbenes (NHC) offers a convenient method to introduce new functionality at the backbone of an NHC. The 4-phosphino-substituted NHC (1a) derived from 1,3-dimesitylimidazol-2-ylidene (IMes) and MesP═CPh₂ is shown to be an effective bifunctional ligand for Au(I) and Pd(II). Several new complexes are reported: 2a: 1a·Au_CCl, 3a: 1a·(AuCl)₂, 4a: [(1a)₂Au_C]Cl, 5a: [(1a·Au_PCl)₂Au_C]Cl], and 6a: 1a·(Pd_C) (Au_PCl). The reaction of 4-phosphino-NHC 1b, derived from 1,3-di(cyclohexyl)imidazol-2-ylidene (ICy) and MesP═C(4-C₆H₄F)₂, with (tht)AuCl (2 equiv, tht = tetrahydrothiophene) affords the fascinating tetranuclear 5b [(1b·Au_PCl)₂Au_C][AuCl₂]. The molecular structure of 5b features a close Au···Au contact (3.0988(4) Å) between the bis(carbene)gold(I) cation and the dichloroaurate(I) anion. The buried volumes (%V_bur) and Tolman cone angles for representative 4-phosphino-NHCs calculated from structural data are compared to related carbenes and phosphines. The molecular structures are reported for complexes 3a, 4a, 5b, and 6a.