Reactivities of organic isothiocyanates and thiocyanates toward dialkyl bis(phosphine) complexes of palladium(II) and platinum(II)

Bimetallic DppfM(II) (M = Pt and Pd) dithiocarbamate complexes: Synthesis, characterization, and anticancer activity

“…The crystallographic details and selected bond distances and angles are presented in Supporting Information (Tables S1 and S2, respectively). The Pd-P bond and Pd-S distances are within the range of those reported for the precursor dppfPdX 2 complexes, 24 other Pd(II) dithiocarbamate complexes, [25][26][27][28][29] and a dppfPd complex with two thiolate ligands, 30 respectively. The S1-Pd-S2 bond angle from the bidentate ligand is 74.99(3)°, which is close to those of typical S1-Pd-S2 angles (75.29°-76.66°).…”

“…The S1-Pd-S2 bond angle from the bidentate ligand is 74.99(3)°, which is close to those of typical S1-Pd-S2 angles (75.29°-76.66°). [25][26][27][28][29] However, it is smaller than the S1-Pd-S2 angle (89.64°) of the dppfPd complex with two thiolate ligands. 30 The N(1)-C(35) bond length (1.303(4)) is significantly shorter than a normal C-N bond (1.47 Å) and longer than that of a C=N bond (1.28 Å).…”

Catalytic Production of Isothiocyanates via a Mo(II)/Mo(IV) Cycle for the “Soft” Sulfur Oxidation of Isonitriles

“…Indeed, as Scheme reveals, treatment of a toluene solution of 4 with excess amounts of t BuNCS at the slightly elevated temperature of 65 °C provided a good yield of the CPAM Mo­(IV) dithiocarbonimidate Cp*Mo­[N­( i Pr)­C­(Ph)­N­( i Pr)]­[κ-( S,S )-S 2 C-(N t Bu)] ( 8 ) as an orange crystalline material . The solid-state molecular structure of 8 as determined by single-crystal X-ray analysis is presented in Figure , for which the geometric bond length values (Å) associated with the κ-( S,S )-S 2 CN t Bu fragment are as follows: Mo1–S1, 2.3694(4); Mo1–S2, 2.3763(3); S1–C24, 1.7832(12); S2–C24, 1.7963(12); C24–N3, 1.2631(15) . On the basis of literature precedent, the most likely mechanism for formation of 8 involves SAT from initial coordination of t BuNCS to a Mo­(II) center to form a transient formal Mo­(IV) terminal sulfide through elimination of t BuNC, followed by trapping of this metal sulfide with another 1 equiv of t BuNCS to form the final thermodynamically stable dithiocarbonimidate product .…”

Facial–Meridional Isomerization and Reductive Elimination in [(R2P-o-C6H4)2N]PtMe3 (R = Ph, iPr)

“…Among these, reactions in toluene by the lithiation route (method A) were the least successful. The fac-PtC 3 configuration of fac-[Ph-PNP]PtMe 3 and fac-[iPr-PNP]PtMe 3 is reminiscent of what is known for six-coordinate trihydrocarbylplatinum(IV) complexes, 5a−c,g−j,p,6 including those containing monodentate or chelating ligands having one nitrogen-donor and two phosphorus-donor atoms such as fac-PtEt 2 (CH 2 Ph)(PMe 3 ) 2 (NCS), 11 Both fac-[Ph-PNP]PtMe 3 and fac-[iPr-PNP]PtMe 3 were isolated as yellow crystals in high yields. Allowing a C 6 D 6 solution of fac-[iPr-PNP]PtMe 3 to stand at room temperature led gradually to the evolution of its isomer, i.e., mer-[iPr-PNP]PtMe 3 , in several hours, as indicated by its 1 H and 31 P{ 1 H} NMR spectra.…”

“…Among these, reactions in toluene by the lithiation route (method A) were the least successful. The fac -PtC 3 configuration of fac -[Ph-PNP]­PtMe 3 and fac -[ i Pr-PNP]­PtMe 3 is reminiscent of what is known for six-coordinate trihydrocarbylplatinum­(IV) complexes, − ,− ,, including those containing monodentate or chelating ligands having one nitrogen-donor and two phosphorus-donor atoms such as fac -PtEt 2 (CH 2 Ph)­(PMe 3 ) 2 (NCS), fac -[PtMe 2 (CCSiMe 3 )­(dmpe)­(solv)]­(OTf) (solv = NCMe, py), fac -PtMe 3 (dppbz)­(NHSO 2 R) [dppbz = o -bis­(diphenylphosphino)­benzene; R = 4-C 6 H 4 n Bu, 4-tolyl], fac -[PtMe 3 (dppe)­(py)]­OTf, fac -[PtMe 3 (Ph 2 PCH 2 C­( t Bu)NNC­( t Bu)­CH 2 PPh 2 )]­PF 6 , fac -PtMe 3 (Ph 2 PCHC­( t Bu)­NNC­( t Bu)­CH 2 PPh 2 ), fac -[PtMe 3 (PMe 2 Ph) 2 (NCMe)]­I, and fac -PtMe 3 (PMe 2 Ph) 2 (NO 2 )…”