Heterotrimetallic Complexes [{Pt(RNH₂)₂(μ‐NHCOtBu)₂}₂M](ClO₄)_n (M = Mn, Co, Cu, Ni, Cd, and Zn, n = 2; M = In, n = 3), [{Pt(NH₃)(μ‐DACHCOtBu)(μ‐NHCOtBu)}₂Ni](ClO₄)₂, and [{Pt(RNH₂)₂(NHCOtBu)₂}₃Ag₃](ClO₄)₃ Bridged by Amidate Ligands: A Novel Amidate−Amine Interligand Reaction

Activation of Homolytic SiZn and SiHg Bond Cleavage, Mediated by a Pt0 Complex, via Novel PtZn and PtHg Compounds

“…[2] Fischer et al reported an umber of novel {PtÀZnCp*} (Cp* = pentamethylcyclopentadienyl) complexes in which ad ivalent zinc is bonded directly to platinum. [4] Herein we report that thermally stable SiÀZn and SiÀHg bonds are activated towards homolytic cleavage by aP t 0 complex, [(dmpe)Pt(PEt 3 ) 2 ]( 1)d mpe = 1,2-bis(dimethylphosphanyl)ethane,y ielding hexacoordinate Pt isomers 2a and 2b (M = Zn) or 3a, 3b (M = Hg), respectively,h aving aP t ÀMSiR 3 moiety [Eq. [4] Herein we report that thermally stable SiÀZn and SiÀHg bonds are activated towards homolytic cleavage by aP t 0 complex, [(dmpe)Pt(PEt 3 ) 2 ]( 1)d mpe = 1,2-bis(dimethylphosphanyl)ethane,y ielding hexacoordinate Pt isomers 2a and 2b (M = Zn) or 3a, 3b (M = Hg), respectively,h aving aP t ÀMSiR 3 moiety [Eq.…”

“…[2][3][4] Several methodologies are available for their synthesis.O ne involves the formation of PtÀZn heteronuclear dative linkages from Lewis basic and Lewis acidic metals (termed metal-only Lewis pairs (MOLPs)). The reaction proceeds via hexacoordinate Pt complexes,( M= Zn (2a and 2b), M = Hg (3a and 3b)) which were isolated and characterized.…”

“…The reaction proceeds via hexacoordinate Pt complexes,( M= Zn (2a and 2b), M = Hg (3a and 3b)) which were isolated and characterized. [4] Herein we report that thermally stable SiÀZn and SiÀHg bonds are activated towards homolytic cleavage by aP t 0 complex, [(dmpe)Pt(PEt 3 ) 2 ]( 1)d mpe = 1,2-bis(dimethylphosphanyl)ethane,y ielding hexacoordinate Pt isomers 2a and 2b (M = Zn) or 3a, 3b (M = Hg), respectively,h aving aP t ÀMSiR 3 moiety [Eq. [1] More specifically,r ecently heterometallic complexes containing Pt and Zn atoms attracted attention and several were isolated.…”

“…[1] More specifically,r ecently heterometallic complexes containing Pt and Zn atoms attracted attention and several were isolated. [4] Herein we report that thermally stable SiÀZn and SiÀHg bonds are activated towards homolytic cleavage by aP t 0 complex, [(dmpe)Pt(PEt 3 ) 2 ]( 1)d mpe = 1,2-bis(dimethylphosphanyl)ethane,y ielding hexacoordinate Pt isomers 2a and 2b (M = Zn) or 3a, 3b (M = Hg), respectively,h aving aP t ÀMSiR 3 moiety [Eq. [1a] Fore xample, recently aM OLP Pt À Zn complex was isolated from the reaction of [Pt(PCy 3 ) 2 ]( Cy = cyclohexyl) and ZnBr 2 .…”

Activation of Homolytic SiZn and SiHg Bond Cleavage, Mediated by a Pt0 Complex, via Novel PtZn and PtHg Compounds

“…[3] Complexes in which Pt and Zn are bridged by ligands were also isolated and characterized. [4] Herein we report that thermally stable SiÀZn and SiÀHg bonds are activated towards homolytic cleavage by aP t 0 complex, [(dmpe)Pt(PEt 3 ) 2 ]( 1)d mpe = 1,2-bis(dimethylphosphanyl)ethane,y ielding hexacoordinate Pt isomers 2a and 2b (M = Zn) or 3a, 3b (M = Hg), respectively,h aving aP t ÀMSiR 3 moiety [Eq.(1)].T hese novel hexacoordinate PtÀMSiR 3 compounds were isolated and characterized by Xray crystallography and their photolysis and thermolysis is reported. Photolysis of 2 (i.e., the obtained 63:37 mixture of 2a+ 2b,respectively) or of 3 (i.e., the obtained 26:74 mixture of 3a+ 3b,r espectively) yields quantitatively the tetracoordinate platinum complex 4 and the EPR spectra of the intermediate pentacoordinate platinum paramagnetic species, 5 (M = Zn) or 6 (M = Hg), respectively,a re observed [Eq.…”