Department of Chemistry, Imperial College London, South Kensington Campus, London, UK SW7 2AZ.
Dalton Trans. 2010 May 7;39(17):4080-9. doi: 10.1039/b925536b. Epub 2010 Mar 11.
The complex cis-[RuCl(2)(dppm)(2)] reacts with the amine-terminated dithiocarbamates KS(2)CN(CH(2)CH(2)NEt(2))(2) and KS(2)CN(CH(2)CH(2)CH(2)NMe(2))(2) to form the compounds Ru{S(2)CN(CH(2)CH(2)NEt(2))(2)}(dppm)(2) and Ru{S(2)CN(CH(2)CH(2)CH(2)NMe(2))(2)}(dppm)(2), respectively. The methoxy-terminated dithiocarbamate compound Ru{S(2)CN(CH(2)CH(2)OMe)(2)}(dppm)(2) was also prepared from the same precursor using KS(2)CN(CH(2)CH(2)OMe)(2). The alkenyl complexes [RuRCl(CO)(BTD)(PPh(3))(2)] (R = CH=CHBu(t), CH=CHC(6)H(4)Me-4, CH=CHCPh(2)OH), [Ru(C(C[triple bond]CBu(t))=CHBu(t))Cl(CO)(PPh(3))(2)] and [Os(CH=CHC(6)H(4)Me-4)Cl(CO)(BTD)(PPh(3))(2)] also react cleanly with KS(2)CN(CH(2)CH(2)CH(2)NMe(2))(2) and KS(2)CN(CH(2)CH(2)NEt(2))(2) to yield [MR{S(2)CN(CH(2)CH(2)CH(2)NMe(2))(2)}(CO)(PPh(3))(2)] and [MR{S(2)CN(CH(2)CH(2)NEt(2))(2)}(CO)(PPh(3))(2)], respectively. In a similar fashion, the compounds [RuR{S(2)CN(CH(2)CH(2)OMe(2))(2)}(CO)(PPh(3))(2)] (R = CH=CHBu(t), CH=CHC(6)H(4)Me-4, C(C[triple bond]CBu(t))=CHBu(t)) were also prepared. Treatment of [Ru(CH=CHBu(t)){S(2)CN(CH(2)CH(2)CH(2)NMe(2))(2)}(CO)(PPh(3))(2)] and Ru{S(2)CN(CH(2)CH(2)NEt(2))(2)}(dppm)(2) with trifluoroacetic acid affords the ammonium complexes Ru(CH=CHBu(t)){S(2)CN(CH(2)CH(2)CH(2)NHMe(2))(2)}(CO)(PPh(3))(2) and Ru{S(2)CN(CH(2)CH(2)NHEt(2))(2)}(dppm)(2), while the same reagent generates the tricationic vinylcarbene complex Ru(=CHCH=CPh(2)){S(2)CN(CH(2)CH(2)CH(2)NHMe(2))(2)}(CO)(PPh(3))(2) through loss of water from [Ru(CH=CHCPh(2)OH){S(2)CN(CH(2)CH(2)CH(2)NMe(2))(2)}(CO)(PPh(3))(2)]. The structures of [Ru{S(2)CN(CH(2)CH(2)OMe)(2)}(dppm)(2)]PF(6) and [Ru(CH=CHC(6)H(4)Me-4){S(2)CN(CH(2)CH(2)OMe)(2)}(CO)(PPh(3))(2)] were determined crystallographically.
顺式-[RuCl2(dppm)2]与端基为二硫代氨基甲酸盐的 KS(2)CN(CH(2)CH(2)NEt(2))(2)和 KS(2)CN(CH(2)CH(2)CH(2)NMe(2))(2)反应，形成化合物[Ru{S(2)CN(CH(2)CH(2)NEt(2))(2)}(dppm)(2)]+和[Ru{S(2)CN(CH(2)CH(2)CH(2)NMe(2))(2)}(dppm)(2)]+。同样地，用 KS(2)CN(CH(2)CH(2)OMe)(2)制备了甲氧端基二硫代氨基甲酸盐化合物[Ru{S(2)CN(CH(2)CH(2)OMe)(2)}(dppm)(2)]+。烯烃配合物[RuRCl(CO)(BTD)(PPh(3))(2)]（R=CH=CHBu(t)，CH=CHC(6)H(4)Me-4，CH=CHCPh(2)OH），[Ru(C(C[三重键]CBu(t))=CHBu(t))Cl(CO)(PPh(3))(2)]和[Os(CH=CHC(6)H(4)Me-4)Cl(CO)(BTD)(PPh(3))(2)]也与 KS(2)CN(CH(2)CH(2)CH(2)NMe(2))(2)和 KS(2)CN(CH(2)CH(2)NEt(2))(2)反应生成[MR{S(2)CN(CH(2)CH(2)CH(2)NMe(2))(2)}(CO)(PPh(3))(2)]和[MR{S(2)CN(CH(2)CH(2)NEt(2))(2)}(CO)(PPh(3))(2)]。类似地，还制备了化合物[RuR{S(2)CN(CH(2)CH(2)OMe(2))(2)}(CO)(PPh(3))(2)]（R=CH=CHBu(t)，CH=CHC(6)H(4)Me-4，C(C[三重键]CBu(t))=CHBu(t)）。用三氟乙酸处理[Ru(CH=CHBu(t)){S(2)CN(CH(2)CH(2)CH(2)NMe(2))(2)}(CO)(PPh(3))(2)]和[Ru{S(2)CN(CH(2)CH(2)NEt(2))(2)}(dppm)(2)]+生成铵配合物Ru(CH=CHBu(t)){S(2)CN(CH(2)CH(2)CH(2)NHMe(2))(2)}(CO)(PPh(3))(2)和Ru{S(2)CN(CH(2)CH(2)NHEt(2))(2)}(dppm)(2)，而相同的试剂通过从[Ru(CH=CHCPh(2)OH){S(2)CN(CH(2)CH(2)CH(2)NMe(2))(2)}(CO)(PPh(3))(2)]中失去水生成三价乙烯基卡宾配合物Ru(=CHCH=CPh(2)){S(2)CN(CH(2)CH(2)CH(2)NHMe(2))(2)}(CO)(PPh(3))(2)。通过晶体学确定了[Ru{S(2)CN(CH(2)CH(2)OMe)(2)}(dppm)(2)]PF(6)和[Ru(CH=CHC(6)H(4)Me-4){S(2)CN(CH(2)CH(2)OMe)(2)}(CO)(PPh(3))(2)]的结构。
