14640-28-9Relevant academic research and scientific papers
Preparation and structural characterization of 1,4-digerma-2-buten-1,4- diylplatinum(II) complexes and their reactions with alkynes, carbon monoxide, and isocyanides
Mochida, Kunio,Karube, Hironori,Nanjo, Masato,Nakadaira, Yasuhiro
, p. 4734 - 4741 (2008/10/09)
1,4-Digerma-2-buten-1,4-diylplatinum(II) complexes were prepared by treatment of a (η-ethylene)(triphenylphosphine)platinum(0) complex with (Z)-α,β-bis(dialkylgermyl)styrenes, and their structures were determined by spectroscopic analysis coupled with X-ray diffraction methods. Thermolysis of 1,4-digerma-2-buten-1,4-diylplatinum(II) complexes afforded linear and cyclic trigermanes and a dinuclear platinum complex. The 1,4-digerma-2-buten-1,4-diylplatinum(II) complexes reacted with alkynes to give the corresponding insertion products, cyclic germy(germylvinyl)platinum(II) species, whose structures have been determined by spectroscopic analysis. The cyclic germy(germylvinyl)platinum(II) complexes were found to easily liberate 1,4-digermacyclohexa-2,5-dienes and a platinum(O) complex. The reactions of 1,4-digerma-2-buten-1,4-diylplatinum(II) complexes with carbon monoxide and isocyanides afforded the corresponding platinum complexes containing one carbon monoxide and one isocyanide ligand, respectively.
Preparation, structural characterization of 1,2-digermacyclobut-3-enes, and their palladium-catalyzed insertion of alkynes
Mochida, Kunio,Karube, Hironori,Nanjo, Masato,Nakadaira, Yasuhiro
, p. 2967 - 2974 (2007/10/03)
1,2-Digermacyclobut-3-enes were prepared by the treatment of Z-α,β-bis(chlorodialkylgermyl)ethenes with Na metal in boiling toluene and their structures were fully established by spectroscopic methods coupled with X-ray crystallography. In the presence of an appropriate catalyst, 1,2-digermacyclobut-3-enes reacted smoothly with alkynes to give the corresponding insertion products, 1,4-digermacyclohexa-2,5-dienes in moderate to good yields. Conventional complexes, such as [Pd(PPh3)4] and [Pt(PPh3)4], serve as efficient catalysts. The mechanism of the insertion reaction of alkynes into the germanium-germanium bond of 1,2-digermacyclobut-3-enes is discussed in terms of a key intermediate, a 1,4-digerma-2-buten-1,4-diylpalladium.
Reactions of binuclear ruthenium-platinum μ-allenyl complexes with nucleophilic and electrophilic reagents. The characterization of two 1:1 adducts of L(PPh3)Pt(μ-η1:η2α,β-C(Ph)=C=CH2)Ru(CO)Cp (L=PPh3, t-BuNC) and p-toluenesulfonyl isocyanate
Willis, Richard R.,Calligaris, Mario,Faleschini, Paolo,Gallucci, Judith C.,Wojcicki, Andrew
, p. 465 - 478 (2007/10/03)
Reactions of (PPh3)2Pt(μ-η1:η2α,β-C(R)=C=CH2)Ru(CO)Cp (R=H (1), Ph (2)) with Ph2PCH2CH2CH2PPh2, PEt3 and t-BuNC in THF at -78°C to room temperature afforded the substitution products L2Pt(μ-η1:η2α,β-C(R)=C=CH2)Ru(CO)Cp (R=H, L2=Ph2PCH2CH2CH2PPh2 (3), R=Ph, L2=Ph2PCH2CH2CH2PPh2 (4), R=H, L2=2PEt3 (5), R=Ph, L2=PPh3 and t-BuNC (6)). No reaction was observed for 1 with Et2NH or C6H11NH2 and 2 with p-TolS(O)2NH2 in THF at reflux temperature. Complex 2 reacted with p-TolS(O)2NCO (TSI) in toluene at -78°C to room temperature to yield two 1:1 addition products of the reactants: the γ-carbon substituted μ-allenyl (PPh3)2Pt(μ-η1:η2α,β-C(Ph)=C=CHC(O)NHS(O)2Tol-p) (7) and the [3+2] cycloadduct (PPh3)2Pt(μ-η1:η2-C=C(Ph)N(S(O)2Tol-p)C(O)CH2)Ru(CO)Cp (8). Complexes 4 and 6 afforded with TSI, under essentially similar conditions, only [3+2] cycloadducts, L2Pt(μ-η1:η2-C=C(Ph)N(S(O)2Tol-p)C(O)CH2)Ru(CO)Cp (L2=Ph2PCH2CH2CH2PPh2 (9), PPh3 and t-BuNC (10)). All products were characterized by a combination of IR and NMR (1H, 13C{1H} and 31P{1H}) spectroscopy, FAB MS and elemental analysis. The structures of 7 (as 7·C3H6O) and 10 were determined by single-crystal X-ray diffraction analysis. Reactions of 2 with trans-NCCH=CHCN (L) and of 1 with the alkynes MeO2CC?CCO2Me, MeO2CC?CMe, PhC?CH and PhC?CPh (L) resulted in the formation of the mononuclear metal complexes Cp(CO)2RuC(R)=C=CH2 (R=H, Ph) and (PPh3)2PtL. The reverse of this fragmentation reaction occurred when Cp(CO)2RuCH=C=CH2 was treated with (PPh3)2Pt(PhC?CPh). No reaction was observed between 2 and each (CN)2C=CPh2 and MeS(O)2NSO in benzene or toluene on heating. The η1-allenyl Cp(CO)2RuC(Ph)=C=CH2, obtained in this study, is a new compound.
Platinum-complex-catalyzed dehydrogenative double silylation of acetylenes, dienes, and olefins with bis(hydrosilane) compounds
Tanaka, Masato,Uchimaru, Yuko,Lautenschlager, Hans-Jürgen
, p. 16 - 18 (2008/10/08)
Acetylenes, dienes, and olefins underwent dehydrogenative double silylation with bis(hydrosilane) species in the presence of platinum complex catalysts to give disilacyclic compounds in good yields.
SYNTHESIS OF CIS-CR)2(PPh3)2> AND TRANS-CR)(PPh3)2> COMPLEXES. CRYSTAL AND MOLECULAR STRUCTURES OF CIS-CC(OH)Me2>2(PPh3)2>*H2O, TRANS-CC(OH)Me2>(PPh3)2>*0.5PhMe, AND TRANS-CC(OH)MeEt>(PPh3)2>*Me2CO. INFLUENCE OF BASES AND THEIR CONCENTRATI...
Furlani, Anita,Licoccia, Silvia,Russo, Maria V.,Villa, Angiola Chiesi,Guastini, Carlo
, p. 2197 - 2206 (2007/10/02)
Complexes cis-CR)2(PPh3)2> can be obtained from cis- and HCCR in 30 percent aqueous ammonia as solvent.Complexes trans-CR)(PPh3)2> are obtained by using chloroform (or dichloromethane)-diethylamine as solvent.No dehydration reactions of the acetylenic alcohols are observed.X-ray analyses on cis-CC(OH)Me2>2(PPh3)2>*H2O, trans-CC(OH)Me2>(PPh3)2>*0.5PhMe, and trans-CC(OH)MeEt>(PPh3)2>*Me2CO revealed in the cis complex the presence of a water molecule forming two strong hydrogen bond with the two cis-oriented hydroxy-groups of the acetylide ligands.In all the complexes the co-ordination around platinum is distorted square planar with the acetylide ligands ?-bonded to platinum.Crystallographic details: cis-CC(OH)Me2>2(PPh3)2>*H2O, monoclinic, space group P21/c, with a = 15.473(5), b = 21.725(6), c = 13.439(4) Angstroem, β = 113.95(3)deg, and Z = 4; R 0.052 for 3 110 observed reflections; trans-CC(OH)Me2>(PPh3)2>*0.5PhMe, triclinic, space group P, with a = 11.695(3), b = 19.690(6), c = 9.214(2) Angstroem, α = 101.88(3), β = 104.26(3), γ = 85.55(3)deg, and Z = 2; R = 0.053 for 3 961 observed reflections; CC(OH)MeEt>(PPh3)2>*Me2CO, triclinic, space group P, with a = 15.544(6), b = 12.567(4), c = 11.719(3) Angstroem, α = 91.12(3), β = 105.36(3), γ = 111.39(3)deg, and Z = 2; R = 0.046 for 4 704 observed reflections.The influence of NH3, NHEt2, and H2NNH2 on the reactivity of cis- with monosubstituted acetylenes is discussed.
