cis/trans mixture, dppm = bis(diphenylphosphino)methane) with thiols initially generated cis- and trans- RuH(SR) (dppm)2 with a rate that depends on both the type and concentration of thiol. The higher basicity of the hydride ligands in 2 (versus 1), which is demonstrated by deuterium exchange with CD3OD, gives rise in the thiol reaction to an initial protonation step prior to loss of H2. A species detected
                                    动能和激活参数数据的反应CCT -Ru(H)2(CO)2(PPH 3)2(1)(CCT =顺式,顺式,反式)的THF与
硫醇,CO和PPH 3,得到CCT - RuH(SR)(CO)2(PPh 3)2,Ru(CO)3(PPh 3)2和Ru(CO)2(PPh 3)2分别显示了一个共同的速率确定步骤,即初始解离的H2从1 ; 活化的复合大概类似于相应的Ru(η 2 -H 2)的物种。Ru(H)2(
DPPM)2(2)(作为顺式/反式混合物,
DPPM =双(
二苯基膦基)
甲烷)与
硫醇的反应最初以速率生成顺式和反式RuH(SR)(
DPPM)2这取决于
硫醇的类型和浓度。2中的
氢化物配体具有更高的碱性(相对于1),这可以通过与CD 3进行
氘交换来证明OD在损失H 2之前使
硫醇反应增加到初始质子化步骤。在检测到一个物种
硫醇反应可能是[期RuH(η 2 -H 2(
DPPM)2 ] 2,预期该反应的和用于与醇的氢交换中间体。的较长反应2用的PhCH