Metal Ion Mediated Transfer and Cleavage of Diaminocarbene Ligands

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• 作者：Rong-Zhi Ku ; Jen-Chung Huang ; Jian-Yang Cho ; Fu-Mei Kiang ; K. Rajender Reddy ; Yi-Chun Chen ; Kuo-Jeng Lee ; Jung-Hua Lee ; Gene-Hsiang Lee ; Shie-Ming Peng ; and Shiuh-Tzung Liu
• 刊名：Organometallics
• 出版年：1999
• 出版时间：May 24, 1999
• 年：1999
• 卷：18
• 期：11
• 页码：2145 - 2154
• 全文大小：294K
• 年卷期：v.18,no.11(May 24, 1999)
• ISSN：1520-6041

文摘

Under mild conditions, reactions of (CO)₅M=C[N(R)CH₂]₂ [M = W, Mo, Cr; R = Et, allyl,benzyl, 4-pentenyl] with (PhCN)₂PdCl₂, (PhCN)₂PtCl₂, [(CO)₂RhCl]₂, (Me₂S)AuCl, [(CH₃CN)₄Cu]BF₄, and AgBF₄ provide the corresponding diaminocarbene complexes via carbeneligand transfer. The resulting Pd(II), Pt(II), Rh(I), and Au(I) carbene complexes are stableand were isolated. The Cu(I) and Ag(I) complexes readily undergo acid-induced M=C cleavageto yield the imidazolidin-2-ylidinium salts. The carbene-transfer reactions were studied fortwo phosphine donors: (CO)_m(L)W=C[N(R)CH₂]₂ {R = Et, benzyl; L = PPh₃, m = 4; L =dppe, m = 3}. The X-ray crystal structures of (CO)₅W=C[N(CH₂C₆H₅)CH₂]₂ (1c), cis-(CO)₄(PPh₃)W=C[N(CH₂C₆H₅)CH₂]₂ (5b), fac-(CO)₃(dppe)W=C[N(CH₂C₆H₅)CH₂]₂ (6b), Cl₂(CO)Pt=C[N(CH₂C₆H₅)CH₂]₂ (9c), and cis-Cl₂Pt{=C[N(CH₂C₆H₅)CH₂]₂}₂ (11b) are reported.