69101-79-7Relevant academic research and scientific papers
Synthesis of heterodinuclear hydride complexes by oxidative addition of a transition-metal hydride to Pt(0) and Pd(0) complexes
Komine, Nobuyuki,Kuramoto, Ayako,Yasuda, Toshiyuki,Kawabata, Tatsuya,Hirano, Masafumi,Komiya, Sanshiro
, p. 194 - 205 (2015/08/18)
Abstract Heterodinuclear hydridoplatinum and -palladium complexes, (dppe)HPt-MLn (MLn = MoCp(CO)3 (3a), WCp(CO)3 (3b)), (dppe)Pt(μ-H)(μ-CO)Mn(CO)4 (3c), (dppe)Pt(μ-H)(μ-CO)FeCp(CO) (3d), cis-L′2HPt-MLn (5aa: LE' = PPh3; MLn = MoCp(CO)3, 5ba: LE' = PPh3; MLn = WCp(CO)3, 5ab: LE' = PMePh2; MLn = MoCp(CO)3, 5ac: LE' = PMe2Ph; MLn = MoCp(CO)3), (dppe)Pd(μ-H)(μ-CO)MLn (MLn = MoCp(CO)2 (7a), WCp(CO)2 (7b)), (dppe)Pd(μ-H)(μ-CO)Mn(CO)4 (7c) are prepared by the oxidative addition of mononuclear transition-metal hydride complexes to zero-valent platinum or palladium complexes. The reactions of the heterodinuclear hydride complexes 3a, 3d and 7a with electron deficient alkenes and alkynes such as dimethyl fumarate or DMAD cause reductive elimination at the Pt or Pd center to give the Pt(alkene or alkyne)(dppe) and MHLn,, suggesting reversibility of this process. The DFT calculations suggest that these reactions are controlled by the thermodynamic stability and the electron rich alkene complex of Pt(0) (or Pd(0)) are preferable to prepare these heterodinuclear hydride complexes by the oxidative addition.
Synthesis and structures of platinum diphenylacetylene and dithiolate complexes bearing diphosphinidenecyclobutene ligands (DPCB-Y)
Nakajima, Yumiko,Nakatani, Mitsuharu,Hayashi, Kyohei,Shiraishi, Yu,Takita, Ryo,Okazaki, Masaaki,Ozawa, Fumiyuki
, p. 1713 - 1722 (2011/01/09)
A series of platinum complexes of the type [Pt(D)(A)] having two kinds of π-conjugated ligand systems with donor and acceptor properties are prepared, using p-substituted diphenylacetylenes (tolan-X; X = OMe, H, CF3), 1,2-benzenedithiolato (bdt) and 1,3-dithia-2-thione-4,5-dithiolato (dmit) as π-donor ligands (D), and 1,2-diaryl-3,4-bis[(2,4,6-tri-tert-butylphenyl) phosphinidene]cyclobutenes (DPCB-Y; diaryl = 2C6H4-p-Y (Y = OMe, H, CF3), biphenyl-2,2′-diyl) as π-acceptor ligands (A). The electronic structures of the resulting complexes are examined in detail to investigate π-orbital interaction occurring in DPCB-Y complexes with a low-coordinate phosphorus ligand. The 31P NMR chemical shifts are highly sensitive to the Pt-P distances of the complexes, and linearly correlated with the bond lengths. The UV-vis absorption spectra of [Pt(tolan-X)(DPCB-Y)] display π-π* transitions in the visible region, which are shifted to longer wavelengths as the electron-donating ability of X and electron-withdrawing ability of Y increase, respectively. The complex [Pt(tolan-OMe)(DPCB-CF3)] with a donor-acceptor combination of substituents exhibits particularly low-energy absorption. The absorption is further red-shifted for [Pt(bdt)(DPCB-phen)] and [Pt(dmit)(DPCB-phen)] having dithiolates as strong π-donor ligands.
Synthesis of hydridoplatinum-molybdenum (or tungsten) heterodinuclear complexes by β-hydrogen elimination of (dppe)EtPt-MCp(CO)3. Selective hydride transfer from Pt to Mo (or W)
Komiya, Sanshiro,Yasuda, Toshiyuki,Fukuoka, Atsushi,Hirano, Masafumi
, p. 63 - 70 (2008/10/08)
Hydridoplatinum-molybdenum (or tungsten) heterodinuclear complexes (dppe)HPt-MCp(CO)3 [M = Mo (1), W (2); dppe = 1,2-bis(diphenylphosphino)ethane] have been prepared by selective β-hydrogen elimination of corresponding ethylplatinum-molybdenum
Photochemical reactions of diphosphineplatinum(II) oxalate complexes
Anderson, Gordon K.,Lumetta, Gregg J.,Siria, Jeffrey W.
, p. 253 - 259 (2007/10/02)
Irradiation at 254 nm of CH3CN/C6H6 or PhCn solutions of produces 2 equiv. of CO2, and in the presence of PhCl or PhI yields .With CO or PhCCPh the products are or CPh)(dppe)>, but in the latter case extended photolysis yields CPh)(dppe)>.Photolysis in the presence of H2 gives a mixture of the + and + cations.Simple elimination of CO2 does not occur in all cases, as illustrated by the formation of when is photolyzed in the presence of methanol.Photochemical reactions of the related complexes (L2 = dppm, dcpe) are also described.
