[RhIr(R)2(μ-CO)(dppm)2] (dppm = μ-Ph2PCH2PPh2; R = CH3 (2), CH2Ph (3)) have been prepared. Both A-frame-like compounds have one alkyl group terminally bound to each metal and a bridging carbonyl ligand. Some subsequent reactivity studies of 2 are reported. Reaction of 2 with CO yields [RhIr(CO)3(dppm)2] and acetone. If this reaction is monitored at low temperature by NMR spectroscopy, the dicarbonyl species [
所述异双二烷基配合物[RhIr(R)2(μ-CO)(
DPPM)2 ](
DPPM =μ-PH 2 PCH 2 PPH 2 ; R = CH 3(2),CH 2 Ph(上3))已制备。两种A-框架样化合物均具有一个与每个
金属末端键合的烷基和一个桥接的羰基
配体。据报道一些后续的2反应性研究。2与CO反应生成[RhIr(CO)3(
DPPM)2 ]和
丙酮。如果在低温下通过NMR光谱监测该反应,则二羰基物质[RhIr(CH 3)2首先观察到(CO)2(
DPPM)2 ](4),然后观察到[RhIr(CH 3)2(CO)3(
DPPM)2 ](5)。在两种产物中,两个甲基均键合至Ir。在CO下加热至环境温度会产生
丙酮和[RhIr(CO)3(
DPPM)2 ]。交叉实验表明,
丙酮主要来自分子内过程。我们建议在Ir上发生CO和甲基的迁移插入。据推测,这种
金属也会发生还原消除。化合物2下进行反应用H 2在-78℃下向[收率RhIrH(CH