38268-63-2Relevant academic research and scientific papers
Preparation and condensation reactions of metal complexes of R2PNSO (R = Me, Ph) with potassium tert-butoxide; X-ray crystal structure of (CO)5Mo(Ph2PNSO)
Chivers, Tristram,Lensink, Cees,Richardson, John F.
, p. 1904 - 1909 (2008/10/08)
The reaction of KNSO with (CO)5M(R2PCl) (M = Cr, Mo; R = Me, Ph) in acetonitrile yields complexes of the type (CO)5M(R2PNSO) (1a-d). An X-ray crystal structure determination of (CO)5Mo(Ph2PNSO) (1d) shows that the Ph2PNSO ligand adopts a cis configuration and is coordinated to molybdenum via the phosphorus atom. Crystal data: monoclinic, space group C2/c, a = 30.236 (3) A, b = 11.034 (1) ?, c = 12.056 (1) ?, β = 96.762 (4)°, V = 3993.9 (6) ?3, Z = 8. The structure was solved by Patterson techniques and refined by full-matrix least squares to give a final R = 0.038 and Rw = 0.030. The bond distances are d(P-N) = 1.699 (5), d(S-N) = 1.501 (6), and d(S-O) = 1.481 (7) ?, and the bond angles at nitrogen and sulfur are 129.2 (4) and 118.6 (3)°, respectively. Complexes la-d react with potassium tert-butoxide in a 2:1 molar ratio to give the homodinuclear complexes (CO)5M(R2PNSNPR2)M(CO)5 (2a-d) in good yields. Treatment of 1a-d with potassium tert-butoxide in a 1:1 molar ratio produces adducts of the type (CO)5M(R2PNS(O)OBu-t)-K+ (3a-d). The reactions of these adducts with (CO)5M′(R2PNSO) (M ≠ M′) or (CO)6M(R′2PNSO) (R ≠ R′) produce symmetrical products in addition to heterodinuclear complexes of R2PNSNPR2 or homodinuclear complexes of the unsymmetrical ligand R2PNSNPR′2, respectively. The mechanism of these condensation reactions of 1a-d in the presence of potassium tert-butoxide is discussed in terms of the product distribution as determined by 31P NMR spectroscopy.
Preparation of molybdenum pentacarbonyl complexes of the Ph2PNSO and Ph2PNSNPPh2 ligands: X-ray crystal structure and fluxional behavior of (CO)5MoP(Ph)2NSN(Ph)2PMo(CO)5
Chivers, Tristram,Lensink, Cees,Richardson, John F.
, p. 819 - 821 (2008/10/08)
The reactions of (CO)5Mo(Ph2PCI) with KNSO or K2SN2 in acetonitrile produce (CO)5Mo(Ph2PNSO) (3a) or (CO)5MoP(Ph)2NSN(Ph)2PMo(CO)5 (4a), respectively. An X-ray crystal structure determination of 4a shows that the Ph2PNSNPPh2 ligand adopts a cis,trans conformation. A variable-temperature 31P NMR spectroscopic study of 4a provides evidence for a cis,trans → trans,cis interconversion (AG?213 = 9.4 ± 0.2 kcal mol-1) in solution.
