922725-08-4

Upstream product

• 196961-63-4 [bis(triphenylphosphoranylidene)ammonium][Ni(CO)(SePh)3] 
• 119327-24-1 2,2',2-trimercapto-3,3',3-tris(trimethylsilyl)triphenylphosphine 

Downstream Products

• 956107-45-2 [Ni(P(o-C₆H₃-3-SiMe₃-2-S)2(o-C₆H₃-3-SiMe₃-2-SH))]2 

Relevant academic research and scientific papers

Mononuclear Ni(II)-thiolate complexes with pendant thiol and dinuclear Ni(III/II)-thiolate complexes with Ni...Ni interaction regulated by the oxidation levels of nickels and the coordinated ligands

Compared to [NiII(SePh)(P(o-C6H3-3- SiMe3-2-S)2(o-C6H3-3-SiMe 3-2-SH))]- (1a) and [NiII(Cl)(P(o-C 6H3-3-SiMe3-2-S)2-(o-C 6H3-3-SiMe3-2-SH))]- (3a) with a combination of the intramolecular [Ni...H-S] and [Ni-S...H-S] interactions, complexes [NiII(SePh)(P(o-C6H 3-3-SiMe3-2-S)2(o-C6H 3-3-SiMe3-2-SH))]- (1b) and [Ni II(Cl)(P (o-C6H3-3-SiMe3-2-S) 2-(o-C6H3-3-SiMe3-2-SH))] - (3b) with intramolecular [Ni...H-S] interaction exhibit lower νS-H stretching frequencies (2137 and 2235 cm-1 for 1b and 3b vs 2250 and 2287 cm-1 for 1a and 3a, respectively) and smaller torsion angles (27.2° for 3b vs 58.9 and 59.1° for 1a and 3a, respectively). The pendant thiol interaction modes of 1a, 3a, and 3b in the solid state are controlled by the solvent pairs of crystallization. Oxygen oxidation of dinuclear [NiII-(P(o-C6H3-3- SiMe3-2-S)2(o-C6H3-3-SiMe 3-2-SH))]2 (4) yielded thermally stable dinuclear [Ni III(P(o-C6H3-3-SiMe3-2-S) 2(o-C6H3-3-SiMe3-2-μ-S))] 2 (5). The two paramagnetic d7 NiIII cores (S = 1/2) with antiferromagnetic coupling (J = -3.13 cm-1) rationalize the diamagnetic property of 5. The fully delocalized mixed-valence [Ni(II)-Ni(III)] complexes [Ni2(P(o-C6H 3-3-SiMe3-2-S)3)2]- (6) and [Ni2(P(o-C6H3-3-SiMe3-2-S) 3)(P(o-C6H3-3-SiMe3-2-S) 2(o-C6H3-3-SiMe3-2-SCH 3))] (7) were isolated upon the reduction of 5 and the methylation of 6, respectively. The electronic perturbation from the sulfur methylation of 6 triggers the stronger Ni...Ni interaction and the geometrical rearrangement from the diamond shape of the [NiS2Ni] core to the butterfly structure of [Ni(μ-S)2Ni] to yield 7 with Ni...Ni distances of 2.6088(1) A. The distinctly different Ni...Ni distances (2.6026(7) for 5 and 2.8289(15) A for 6) and the coordination number of the nickels indicate a balance of geometrical requirements for different oxidation levels of [PS3Ni-NiPS3] cores of 5 and 6.

Mononuclear Ni(III) complexes [NiIII(L)(P(C6H 3-3-SiMe3-2-S)3)]0/1- (L = thiolate, selenolate, CH2CN, Cl, PPh3): Relevance to the nickel site of [NiFe] hydrogenases

The stable mononuclear Ni(III)-thiolate complexes [NiIII(L) (P(C6H3-3-SiMe3-2-S)3)]- (L = SePh (2), Cl (3), SEt (4), 2-S-C4H3S (5), CH 2CN (7)) were isolated and characterized by UV-vis, EPR, IR, SQUID, CV, 1H NMR, and single-crystal X-ray diffraction. The increased basicity (electronic density) of the nickel center of complexes [Ni III(L)-(P(C6H3-3-SiMe3-2-S) 3)]- modulated by the monodentate ligand L and the substituted groups of the phenylthiolate rings promotes the stability and reactivity. In contrast to the irreversible reduction at -1.17 V (vs Cp 2Fe/Cp2Fe+) for complex 3, the cyclic voltammograms of complexes [NiIII(SePh)(P(o-C6H 4S)3)]-, 2, 4, and 7 display reversible Ni III/II redox processes with E1/2 = -1.20, -1.26, -1.32, and -1.34 V (vs Cp2Fe/Cp2Fe+), respectively. Compared to complex 2 containing a phenylselenolate-coordinated ligand, complex 4 with a stronger electron-donating ethylthiolate coordinated to the Ni(III) promotes dechlorination of CH2Cl2 to yield complex 3 (kobs = (6.01 ± 0.03) × 10-4 s-1 for conversion of complex 4 into 3 vs kobs = (4.78 ± 0.02) × 10-5 s-1 for conversion of complex 2 into 3). Interestingly, addition of CH3CN into complex 3 in the presence of sodium hydride yielded the stable Ni(III)-cyanomethanide complex 7 with a NiIII-CH2CN bond distance of 2.037(3) A. The Ni III-SEt bond length of 2.273(1) A in complex 4 is at the upper end of the 2.12-2.28 A range for the NiIII-S bond lengths of the oxidized-form [NiFe] hydrogenases. In contrast to the inertness of complexes 3 and 7 under CO atmosphere, carbon monoxide triggers the reductive elimination of the monodentate chalcogenolate ligand of complexes 2, 4, and 5 to produce the trigonal bipyramidal complex [NiII(CO)(P(C6H 3-3-SiMe3-2-S)3)]- (6).