The functionalisation of ruthenium(II) and osmium(II) alkenyl complexes with amine- and alkoxy-terminated dithiocarbamates.
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)](2+) and [Ru{S(2)CN(CH(2)CH(2)NHEt(2))(2)}(dppm)(2)](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)](3+) 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.
Naeem
Saira
S
Department of Chemistry, Imperial College London, South Kensington Campus, London, UK SW7 2AZ.
Ogilvie
Eleanor
E
White
Andrew J P
AJ
Hogarth
Graeme
G
Wilton-Ely
James D E T
JD