90667-70-2Relevant academic research and scientific papers
Si-Si and Si-O bond activation at platinum: Stepwise formation of a SiH3 complex
Mitzenheim, Catherine,Braun, Thomas
, p. 8625 - 8628 (2013/09/12)
The more, the better: Treatment of [Pt(H)2(dcpe)] (dcpe=1,2-bis(dicyclohexylphosphino)ethane) with stoichiometric amounts of silane leads to the bis(silyl) complex [Pt{Si(OMe)3} 2(dcpe)], whereas the use of an excess silane results in hydrodealkoxylations by repetitive Si-O bond activation and the formation of SiH3 ligands (see scheme; Cy=cyclohexyl). Copyright
Chemistry of phosphine-borane adducts at platinum centers: Dehydrocoupling reactivity of Pt(II) dihydrides with P-H bonds
Jaska, Cory A.,Lough, Alan J.,Manners, Ian
, p. 326 - 331 (2007/10/03)
The reaction of the Pt(II) dihydride complex cis-[PtH2(dcype)] (dcype = 1,2-bis(dicyclohexylphosphino)ethane) with the primary or secondary phosphine-borane adducts PhRPH·BH3 (R = H, Ph) was found to exclusively afford the mono-substituted complexes cis-[PtH(PPhR·BH 3)(dcype)] (1: R = H; 2: R = Ph) via a dehydrocoupling reaction between Pt-H and P-H bonds. Similar reactivity was observed between the uncoordinated phosphines PhRPH (R = H, Ph) and cis-[PtH2(dcype)], which gave cis-[PtH(PPhR)(dcype)] (4: R = H; 5: R = Ph). The complexes were characterized by 1H, 11B, 13C and 31P NMR spectroscopy, IR, MS and, in the case of 2, X-ray crystallography that confirmed the cis geometries. The di-substituted complex cis-[Pt(PhPH·BH3)2(dcype)] 3) was prepared from the reaction of cis-[PtCl2(dcype)] with two equivalents of Li[PPhH·BH3]. This suggested that steric reasons alone cannot be used to explain the lack of reactivity with respect to a second dehydrocoupling reaction involving the remaining Pt-H bond in complexes 1, 2, 4 and 5.
Binuclear Hydridoplatinum(II): One-Pot Synthesis, INS Spectra and X-ray Crystal Structure of [Pt2(dcype)2(H)3][BPh 4] {dcype = 1,2-Bis(dicyclohexylphosphanyl)ethane}
Bandini, Anna Laura,Banditelli, Guido,Manassero, Mario,Albinati, Alberto,Colognesi, Daniele,Eckert, Juergen
, p. 3958 - 3967 (2007/10/03)
The binuclear platinum(II) hydride [Pt2(dcype) 2(H)3][Cl] (1b) has been isolated in high yields by treatment of Pt(dcype)Cl2 with NaBH4 (molar ratio 1:2) in ethanol solution at room temperature. This one-pot synthesis is not straightforward when starting from diphenylphosphanylalkane complexes. The compounds [Pt2(dppp)2(H)3][OH] (3b) and [Pt2(dppb)2(H)3][OH] (4) were isolated by starting from the mononuclear hydrides {cis-[Pt(P-P)(H)2]} while mixtures of both binuclear {[Pt2(dppe)2(H) 3]+, 5} and trinuclear {[Pt3(dppe) 3(H)3]+, 6} trihydrides were obtained with the dppe ligand. Various salts of the cation 1, [Pt2(dcype) 2(H)3][X] (X = BF4, 1a; OH, 1c; BPh 4, 1d), were isolated either from [Pt(dcype)(μ-OH)] 2[BF4]2 (2) by a general procedure (1a), or by decomposition of the complex cis-[Pt(dcype)(H)2] in solution (1c), as well as by metathesis reactions (1a, 1c, and 1d). Compounds 1a, 1b, and 1d react with CO under mild conditions to afford the corresponding PtI binuclear hydrides [Pt2(dcype)2(μ-CO)(μ-H)][X] (X = Cl, 7a; BF4, 7b; BPh4, 7c). The binuclear core of cation 1 is broken by KCN in methanol solution, yielding the mononuclear complex cis-[Pt(dcype)(CN)(H)] (8). The complexes 1a-d, 2, 7a-c, and 8 have been characterised by FAB MS, IR, and NMR (1H, 31P, and 195Pt) spectroscopic techniques; the 1 and 7 cations show fluxional behaviour on the NMR timescale. The structure of compound 1d was determined, at 200 K, by single-crystal X-ray diffraction. All the hydrido ligands were located. The Pt-Pt separation is 2.696(1) A and the coordination geometry around each platinum centre can be regarded as distorted square planar. Incoherent Inelastic Neutron Scattering (INS) spectra were obtained for la and [Pt2(dppe)2(H)3][BF4] (5a); the spectra reflect the different geometries of the two "P4Pt 2(H)3" cores as found by single-crystal structure determinations. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
Insertion of Elemental Sulfur and SO2 into the Metal-Hydride and Metal-Carbon Bonds of Platinum Compounds
Morton, Michael S.,Lachicotte, Rene J.,Vicic, David A.,Jones, William D.
, p. 227 - 234 (2008/10/08)
Elemental sulfur (S8) has been found to insert only one sulfur atom into the metal-hydride bonds of the platinum alkyl and aryl hydride complexes [(dcpe)PtRH] (dcpe = Cy2PC2H4-PCy2). Unlike the parent compounds, the S-inserted complexes do not undergo reductive elimination to form the corresponding alkane- or arenethiols. Methane is lost from the methyl sulfhydryl complex. Sulfur dioxide was also found to insert into a platinum-methyl bond to form the corresponding S-bound sulfinate, which upon reacting with mineral acids generates methylsulfinic acid.
Stability of (Chloromethyl)platinum(II) Complexes
McCrindle, Robert,Arsenault, Gilles J.,Gupta, Anuradha,Hampden-Smith, Mark J.,Rice, Richard E.,McAlees, Alan J.
, p. 949 - 954 (2007/10/02)
The stabilities of , (cod = cycloocta-1,5-diene) and a range of phosphine-containing mono- and cis-bis-(chloromethyl)platinum(II) complexes have been investigated in deuteriochloroform at room temperature.Some of the bis(chloromethyl) derivatives appear to be indefinitely stable (cod and chelating arylphosphines), others suffer very slow decomposition to the dichlorides (non-chelating arylphosphines), and the remainder decompose relatively rapidly, and cleanly, to the dichlorides plus ethylene (alkylphosphines, non-chelating faster than chelating).Rapid decomposition of the arylphosphine complexes can be induced by adding hexafluoroisopropyl alcohol to the deuteriochloroform solutions.Attempts to generate 2> by addition of P(C6H11)3 to resulted in the formation of cis--+(C6H11)3>Cl2>; a mechanism is proposed.All cis-mono(chloromethyl) derivatives studied appear to be indefinitely stable.In contrast, the trans-mono(chloromethyl) complexes, although stable in very dry solvent, undergo decomposition in the presence of moisture to the corresponding hydrides plus formaldehyde; a mechanism is proposed.The hydrides undergo subsequent conversion into a mixture of cis and trans dichlorides.
platinum(0). Reactions with Alkyl, (Trimethylsilyl)methyl, Aryl, Benzyl, and Alkynyl Carbon-Hydrogen Bonds
Hackett, Marifaith,Whitesides, George M.
, p. 1449 - 1462 (2007/10/02)
cis-Hydridoneopentylplatinum(II) (1) reductively eliminates neopentane and generates platinum(0) (2).This bent bis(phosphine)platinum(0) complex was not observed directly; its intermediac
MIXED LIGAND COMPLEXES OF PLATINUM(0) CONTAINING DIPHOSPHINES
Clark, Howard C.,Kapoor, Pramesh N.,McMahon, Ian J.
, p. 107 - 116 (2007/10/02)
The reaction of PtCl2L (L = diphosphine) with the appropriate diphosphine L' in ethanol followed by reduction with aqueous sodium borohydride leads to either disproportionation to give mixtures of the bis(diphosphine) complexes PtL2 and PtL'2 or to the fo
