Carbene complexes. Part 13. The synthesis and characterisation of secondary carbene complexes of vanadium(I), chromium(0), molybdenum(0), tungsten(0), manganese(I), rhenium(I), iron(0), ruthenium(II), cobalt(I), iridium(III), and platinum(IV), and hydridorhodium(III)
Carbene complexes. Part 13. The synthesis and characterisation of secondary carbene complexes of vanadium(I), chromium(0), molybdenum(0), tungsten(0), manganese(I), rhenium(I), iron(0), ruthenium(II), cobalt(I), iridium(III), and platinum(IV), and hydridorhodium(III)
复制标题
卡宾配合物。
DOI：
--
复制
发表时间：
1978
期刊：
影响因子：
--
通讯作者：
K. Turner
中科院分区：
文献类型：
--
作者：
A. Hartshorn;M. Lappert;K. Turner
（氯甲基）二甲基氯化铵[NMe2(CHCl)]Cl（或其二溴类似物）是仲碳金属配合物[M{CH(NMe2)}Ln]的方便来源。除了对d8金属配合物（Ru0， lrI或PtII）进行三段氧化加成得到d6加合物外，还开发了另外两种方法：从过渡金属酸盐前驱体（V-I, Cr-II, Mo-II， W-II或Fe-II）中去除盐，以及使用过渡金属酸盐单阴离子前驱体（Mo0, W0, Mn-I， Re-I或Co-I）进行氧化加成去除盐。羰基（III）配合物[{Rh[CH(NMe2)](CO)Cl3}2]在乙醇中与PPh3反应生成氢羰基配合物[Rh{CH(NMe2)}Cl2H (PR3)2](R = Ph)，可得到类似物（R3= Et2或Me2Ph）。利用红外和1H或13C核磁共振光谱对23个新配合物进行了表征，并确定了它们的立体化学性质。
(Chloromethylene)dimethylammonium chloride [NMe2(CHCl)]Cl (or its dibromo-analogue) is a convenient source of secondary carbenemetal complexes [M{CH(NMe2)}Ln]. As well as three-fragment oxidative addition to d8 metal complexes (Ru0, lrI, or PtII) to give d6 adducts, two other procedures have been developed: salt elimination from a transition-metallate dianion precursor (V–I, Cr–II, Mo–II, W–II, or Fe–II), and salt elimination with concomitant oxidative addition using a transition-metallate monoanion precursor (Mo0, W0, Mn–I, Re–I, or Co–I). The carbenerhodium(III) complex [{Rh[CH(NMe2)](CO)Cl3}2] reacts with PPh3 in ethanol to yield the hydridocarbene complex [Rh{CH(NMe2)}Cl2H (PR3)2](R = Ph) from which analogues (R3= Et2 or Me2Ph) are accessible. Infrared and 1H or 13C n.m.r. spectra have been used to characterise the 23 new complexes and establish their stereochemistry.