H2O:MeCN; diminished activity is attributed to deterioration of [Ru(bipy)3]2+. Monitoring of the photolysis mixture by mass spectrometry suggests transformation of [Mo3(μ3-S)(μ2-S2)3(S2CNR2)3]+ to [Mo3(μ3-S)(μ2-S)3(S2CNR2)3]+ via extrusion of sulfur on a time scale of minutes without accumulation of the intermediate [Mo3S6(S2CNR2)3]+ or [Mo3S5(S2CNR2)3]+ species. Deliberate preparation of [Mo3S4(S2CNEt2)3]+
[Mo3(μ3-S)(μ2-S2)3(S2CNR2)3] I([2a] I,R = Me; [2b] I,R = Et; [2c] I,R = iBu; [2d] I,R = CH2C6H5)在以[Ru(bipy)3] 2+作为光敏剂和Et3N作为电子给体的混合
水-极性有机介质中导致H2析出。在1:9
H2O:MeCN中,R = iBu可发现最大活性(300次翻转,3小时);活性降低归因于[Ru(bipy)3] 2+的降低。通过质谱监测光解混合物表明[Mo3(μ3-S)(μ2-S2)3(S2CNR2)3] +转变为[Mo3(μ3-S)(μ2-S)3(S2CNR2)3] +通过在几分钟的时间尺度上挤出
硫而不会积累中间体[Mo3S6(S2CNR2)3] +或[Mo3S5(S2CNR2)3] +物质。故意制备[Mo3S4(S2CNEt2)3] +([3] +)并用Et2
NCS21-处理会产生[M