Metallaheteroborane Chemistry. Part 10. Synthesis and Characterisation of closo-Structured Rhodathiaborane Complexes (L = L' = PPh3; L = PMe2Ph, L' = PMe2Ph of PPh3)

Article abstract of DOI:10.1039/DT9920002865

The reaction of CO with <8,8-(PPh3)2-8,7-RhSB9H10> 1 in benzene yields <8-(CO)-8,8-(PPh3)2-nido-8,7-RhSB9H10> 3 in 98percent yield.Refluxing a benzene solution of 3 produces <1-(CO)-1,3-(PPh3)2-closo-1,2-RhSB9H8> 4 in 46percent yield.The reaction between 4 and excess of PMe2Ph in refluxing benzene affords <1-(CO)-1-(PMe2Ph)-3-L-closo-1,2-RhSB9H9> .NMR data ((1)H, (11)B and (31)P) confirm the nido nature of the 3 and the closo structures of compounds 4-6.X-Ray diffraction studies of 4,4' (= 4*1.5 C6H5Me), and 5 showed that there was conformational disorder in all three cases.The structure of 5 was solved in space group P2₁/n with unit cell dimensions of a = 9.626(2), b = 23.714(5), c = 11.595(2) Angstroem, β = 109.00(2) deg, Z = 4.The final R factor was 0.027 for 4472 observed reflections.Principal interatomic distances are Rh(1)-S(2) 2.3736(7), Rh(1)-P(1) 2.3090(7), Rh(1)-C(1) 1.855(3), Rh(1)-B(3) 2.101(3), Rh(1)-B (4, 5, 6, 7) 2.380(3)-2.444(3), S(2)-B 1.923(3)-1.989(4), B-B 1.719(4)-1.897(4) and B(3)-P(2) 1.895(3) Angstroem.The geometry of the RhSB9 cage in 5 was used as a template in the final refinement of the structures of 4 and 4' which were more disordered: 4, space group C2/c, a = 37.529(11), b = 10.749(5), c = 19.536(5) Angstroem, β = 101.96(2) deg, Z = 8, R 0.051 for 3970 observed reflections; 4', space group P1, a = 11.933(2), b = 14.157(2), c = 14.190(2) Angstroem, α = 79.25(1), β = 83.27(1), γ = 87.32(1) deg, Z = 2, R 0.041 for 6959 observed reflections.

Full text of DOI:10.1039/DT9920002865

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