90668-33-0Relevant articles and documents
Preparation and Properties of Bisdinickel(+1) Ion, a Novel Unsymmetrical Thiolate-bridged Complex
Pfeiffer, Ernst,Pasquier, Maurice L.,Marty, Werner
, p. 654 - 663 (1984)
The title cation( =Ni2L31+ ) is formed in a variety of reactions (Schemes 1 and 2) in systems containing Ni2+ and (2-thiolatoethyl)-diphenylphosphine ( =L- ) in the absence of coordinating anions at Ni2+/L- ratios >0.5 in apolar or moderately polar media.Solid ClO4 and BPh4 have been isolated.Job's plots confirm the Ni2L3+-stoichiometry in solution. 31P-NMR data are consistent with >/= 97 percent Ni2L3+ (vs. 2+) at equilibrium and support the suggested configuration (Fig.2).The equilibrium between NiL2 + NiL2Br2 and Ni2L3+ + Br- varies with the solvent composition in CH2Cl2/EtOH mixtures.The rate of formation of Ni2L2Br2 from Ni2L3+ and bromide (in high excess) in CH2Cl2 is first-order in +>tot but depends on the ratio tot/tot, even at a high excess of bromide.This is interpreted by efficient competition in ion-aggregate formation between the small perchlorate concentration introduced as the counterion of Ni2L3+, and the large excess of bromide.
Light induced sulfur-dealkylation of phosphino-thioether nickel(0) complexes
Kim, Jang Sub,Reibenspies, Joseph H.,Darensbourg, Marcetta Y.
, p. 283 - 294 (2008/10/08)
The observation of homolytic S-CH3 bond cleavage in (Ph2P(o-C6H4)SCH3) 2Ni0 under photochemical conditions has prompted further investigation of nickel(0) complexes and their stability. Tetradentate P2S′2 donor ligands (S′ = thioether type S donor) with aromatic rings incorporated into the P to S links, Ph2P(o-C6H4)S(CH2) 3S(o-C6H4)PPh2 (arom-PSSP), or the S to S links, Ph2P(CH2)2SCH2(o-C6H 4) CH2S (CH2)2PPh2 (PS-xy-SP), have been used to form four-coordinate, square planar nickel (II) complexes, [(arom-PSSP)Ni] (BF4)2 (2) and [(PS-xy-SP)Ni] (BF4)2 (3). The bidentate and tetradentate ligands, Ph2P(o-C6H4)SCH2CH3 (arom-PSEt) and Ph2P(CH2)2S(CH2) 3S(CH2)2PPh2 (PSSP), give similar complexes, [(arom-PSEt)2Ni] (BF4)2 (1) and [(PSSP)Ni] (BF4)2 (4), respectively. Cyclic voltammograms of the NiII complexes in CH3CN show two reversible redox events assigned to NiII/I and NiI/0. The one-electron reduction product produced by stoichiometric amounts of Cp2Co can be characterized by EPR. At 100 K rhombic signals show hyperfine coupling to two phosphorus atoms. Complete bulk chemical reduction of complexes 1, 2, 3 and 4 with Na/Hg amalgam provided the corresponding nickel(0) complexes 1R, 2R, 3R and 4R which were isolated as red solutions or solids and characterized by magnetic resonance properties and reaction products. Photolysis of these nickel(0) complexes leads to S-dealkylation to produce alkyl radicals and dithiolate nickel(II) complexes. Complex 3 crystallized in the monoclinic space group P21/c with a = 20.740(5), b = 9.879(3), c = 17.801(4) ?, β = 92.59(2)°, V = 3644(2) ?3 and Z=4; complex 4: P21 with a = 13.815(4), b = 13.815(4), c = 15.457(5) ?, β = 104.89(2)°, V = 3365.4(14) ?3 and Z = 4.
X-ray structure and solution characterization of Ni(μ-SCH2CH2PPh2)2Mo(CO) 4
Chojnacki, Stephen S.,Hsiao, Yui-May,Darensbourg, Marcetta Y.,Reibenspies, Joseph H.
, p. 3573 - 3576 (2008/10/08)
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