Complexes of molybdenum-(II) and -(IV) and tungsten(II) with sterically hindered thiolate ligands. Synthesis, reactivity, and X-ray crystal structures of [PPH4][Mo(SC6H2Pri 3,-2,4,6)3(CO)2] and [Mo(NNPh)(SC6H2Pri 3-2,4,6)3(NCMe)]

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Abstract
[MBr2(CO)4](M = MO or W) react with thiolate anions SR– to give the anions [M(SR)3(CO)2]–(SR = SC6H2Pri 3-2,4,6, SC6H3Pri 2-2,6, SC6H2Br-4-Pri 2-2,6, SC6H2Me3–2,4,6, SC6F5). The complex [pph4][Mo(SC6H2Pri 3-2,4,6)3(CO)2] crystallises in space group P with a= 13.451 (2), b= 14.229(2), c= 19.862(3)Å, α= 96.11(1), β= 94.11(1), γ= 111.04(1)°, and Z= 2. Structure analysis based on 2 939 reflections with I0 < 3.0σ(I0) refined to R= 0.0755. The anion has a trigonal-bipyramidal structure with axial co-ligands. The complexes [M (SR)3(CO)2]– react with CO to give [M(SR)3(CO)3]–. [Mo(SC6H2Pri 3-2,4,6)3(CO)2]– reacts with neutral donors L to give [Mo(SC6H2Pri 3-2,4,6)3(CO)L]–(L = MeCN, ButCN, PMe2Ph, or ButNC) and with [N2Ph][BF4] in MeCN to give [Mo(NNPh)(SC6H2Pri 3-2,4,6)3(NCMe)]. This complex crystallises in space group Pnma with a= 9.962(3), b= 21.002(4), c= 27.646(4)Å, and Z= 4. Structure analysis based on 1 772 reflections with I0 > 3σ(I0) refined to R= 0.075. The NNPh and MeCN ligands occupy the axial sites of a trigonal bipyramid with the thiolates equatorial.