%0 Generic
%A Adams, Richard D.
%A Captain, Burjor
%A Pellechia, Perry J.
%A Zhu, Lei
%D 2004
%T Addition of Pt(PBut3) Groups to Ru5(CO)12(η6-C6H6)(μ5-C). Synthesis,
Structures, and Dynamical Activity
%U https://acs.figshare.com/articles/dataset/Addition_of_Pt_PBu_sup_t_sup_sub_3_sub_Groups_to_Ru_sub_5_sub_CO_sub_12_sub_sup_6_sup_C_sub_6_sub_H_sub_6_sub_sub_5_sub_C_Synthesis_Structures_and_Dynamical_Activity/3318118
%R 10.1021/ic049004l.s004
%2 https://acs.figshare.com/ndownloader/files/5156884
%K mol
%K products Ru 5
%K Ru 5
%K kcal
%K CO
%K Compound 8
%K NMR time scale
%K Ru 5 Pt metal core
%K Ru 5 Pt octahedron
%X The reaction of Ru5(CO)12(η6-C6H6)(μ5-C), 7, with Pt(PBut3)2 yielded two products Ru5(CO)12(η6-C6H6)(μ6-C)[Pt(PBut3)], 8, and Ru5(CO)12(η6-C6H6)(μ6-C)[Pt(PBut3)]2, 9. Compound 8 contains a Ru5Pt metal core in an open
octahedral structure. In solution, 8 exists as a mixture of two isomers that interconvert rapidly on the NMR time
scale at 20 °C, ΔH⧧ = 7.1(1) kcal mol-1, ΔS⧧ = −5.1(6) cal mol-1 K-1, and ΔG298⧧ = 8.6(3) kcal mol-1. Compound
9 is structurally similar to 8, but has an additional Pt(PBut3) group bridging an Ru−Ru edge of the cluster. The two
Pt(PBut3) groups in 9 rapidly exchange on the NMR time scale at 70 °C, ΔH⧧ = 9.2(3) kcal mol-1, ΔS⧧ = −5(1)
cal mol-1 K-1, and ΔG298⧧ = 10.7(7) kcal mol-1. Compound 8 reacts with hydrogen to give the dihydrido complex
Ru5(CO)11(η6-C6H6)(μ6-C)[Pt(PBut3)](μ-H)2, 10, in 59% yield. This compound consists of a closed Ru5Pt octahedron
with two hydride ligands bridging two of the four Pt−Ru bonds.
%I ACS Publications