16633-72-0Relevant academic research and scientific papers
Orthorhombic and Monoclinic Allotropes of cis-, cis-Dichlorobis(methyldiphenylphosphine)platinum(II): Structure Analyses
Kin-Chee, Ho,McLaughlin, George M.,McPartlin, Mary,Robertson, Glen B.
, p. 421 - 425 (1982)
The crystal-structure analysis of two stable allotropes of cis- (C26H26Cl2P2Pt, Mr=666.44) is reported. (I) is orthorhombic, space group P212121 with a = 10.0271(6), b = 14.5578(6), c = 17.0528(8) Angstroem, Z=4, V=2489.24 Angstroem3, Dm=1.77(2), Dc=1.778 Mg m-3, F(000)=1296, μ(Cu Kα)=14.025 mm-1, T=294(1) K. (II) is monoclinic, space group p21/c with a=12.8639(9), b=13.6580(3), c=18.9963(14) Angstroem, β=131.312(6)o, Z=4, V=2506.93 Angstroem3, Dm=1.76(1), Dc=1.766 Mg m-3, F(000)=1296, μ(Cu Kα)=13.926 mm-1, T=294(1) K.Full-matrix least-squares refinements, with fixed H atoms, converged with R = 0.024 for (I) (2296 reflections) and 0.019 for (II) (3220 reflections).Molecules in both allotropes are essentially cis square planar, with similar small tetrahedral deformations of the coordination spheres.In (II) the PMePh2 ligands are disposed less symmetrically than in (I), resulting in inequivalence of the Cl-Pt-P angles o> and of the Pt-Cl distances .The Pt-P distances are equivalent within experimental error .Corresponding mean bond distances for (I) are Pt-P, 2.249(1) and Pt-Cl, 2.350(1) Angstroem.
Group 8 and 10 hyponitrite and dinitrosyl complexes
Arulsamy, Navamoney,Bohle, D. Scott,Imonigie, Jerome A.,Moore, Raecca C.
, p. 4737 - 4745 (2008/10/09)
cis-Hyponitrite complexes LnM(N2O2) (M = Ni, Pt; Ln = PPh3, PPh2Me, dppe, and dppf) of divalent group 10 metals have been previously shown to be readily prepared by treating the corresponding LnMCl2 derivatives with sodium-(Z)-1-{4-(2,6-di-tert-butyl-4-methoxycyclohexadienonyl)}diazen-1-ium-1,2-diolate. These complexes adopt a diamagnetic square planar geometry with oxygen bound chelating planar cis-hyponitrite ligands. They are readily prepared at room temperature but thermally decompose above 90 °C with release of nitrous oxide. Electrophiles such as iodine, methyltriflate, and hydrochloric acid also react rapidly with the cis-hyponitrite complexes to give nitrous oxide. The structure of one of these previously prepared complexes, (PPh3)2Pt(N2O2), has been redetermined at -100 °C as a dichloromethane solvate with improved precision. The related tetrahedral group 8 dinitrosyl complexes, (PPh3)2M(NO)2 (M = Ru, Os; Ln = PPh3, dppe, and dppf) have been reexamined and new derivatives with chelating phosphines have been prepared by ligand substitution on the corresponding (PPh3)2M(NO)2. The structures of Ru(dppf)(NO)2 and Os(dppe)(NO)2 have been determined. These two analogous families of cis-hyponitrite and dinitrosyl complexes illustrate the balance of metal dn electron count and nitrosyl redox state with one having linear nitrosyls bound to low valent metal centers, and the former having coupled N2 O22 - ligands bound to a higher oxidation state metal center.
Multiple coordination modes of hemilabile 3-dimethylaminopropyl chalcogenolates in platinum(II) complexes: Synthesis, spectroscopy and structures
Dey, Sandip,Jain, Vimal K.,Butcher, Ray J.
, p. 2653 - 2660 (2008/10/09)
The reactions of N,N-dimethylaminopropyl chalcogenolates with platinum(II) compounds have been carried out and complexes of the types [PtCl(ECH2CH2CH2NMe2)]2 (1) (E = S (1a) and Se (1b)), [Pt(ECH2CH2CH2NMe2)2]n (2) (E = S (2a) and Se (2b)), [(PtCl2)2{(Me2NCH2CH2CH2E)2}]n (3), [PtX(SeCH2CH2CH2NMe2)]2 (4) (X = SePh (4a) and OAc (4b)) and [PtCl(ECH2CH2CH2NMe2)(PR3)]n (5) (E = S, Se, Te) have been isolated. These complexes have been characterized by elemental analysis, IR, UV-Vis, NMR (1H, 13C, 31P, 77Se, 195Pt) spectroscopy and FAB mass spectral data. The structures of [PtCl(SeCH2CH2CH2NMe2)]2 (1b) and [PtCl(SCH2CH2CH2NMe2)(PPr3)]2 (5a) have been established by single crystal X-ray diffraction data. Both the molecules have dimeric structures. In 1b, two platinum atoms are held together by symmetrically bridging Se atoms of the chelating selenolate groups. In 5a, two thiolates form a four-membered Pt2S2 bridge with dangling NMe2 groups.
Coordination chemistry of P-rich phosphanes and silylphosphanes. XXI [1] the influence of the PR3 ligands on formation and properties of the phosphinophosphinidene complexes [{η2-tBu2P-P}Pt(PR3)
Matern, Eberhard,Pikies, Jerzy,Fritz, Gerhard
, p. 2136 - 2142 (2008/10/08)
(R3P)2PtCl2 and C2H4 yield the compounds [{η2-C2H4}Pt(PR3)2] (PR3 = PMe3, PEt3, PPhEt2, PPh2/su
Substitution and Isomerisation Reactions at Platinum(II) involving Halide, Tertiary Phosphine, Carbonyl, and Isonitrile Ligands
Cross, Ronald J.,Phillips, Ian G.
, p. 2261 - 2264 (2007/10/02)
Carbon monoxide catalyses trans to cis isomerisations of (L = tertiary phosphine) in chloroform solution.The process involves formation of five-co-ordinate intermediates from which halide or tertiary phosphine can be eliminated, giving trans-(1+) or cis- respectively.Structure changes appear to be by pseudo-rotations rather than by consecutive displacements.A number of isonitrile complexes undergo similar reactions.Halide-bridged cations (2+) formed by halide extraction from cis- by Ag(1+) enter rapid (n.m.r. time-scale) exchange processes with the latter complexes at ambient temperatures.Halide elimination from cis- by solvent chloroform appears to initiate the process.The trans isomers do not participate in the exchange.
Reactivity of platinum diolefin complexes. 2. Reactions with bulky and chelating group 5B ligands and studies relating to carbonyl insertion
Anderson,Clark,Davies
, p. 3607 - 3611 (2008/10/08)
Reactions of [PtXY(cod)] (X = Y = Cl, Me, Ph; X = Cl, Y = Ph, COPh) with bulky monodentate and chelating group 5B ligands have been examined by 31P{1H} NMR spectroscopy. The molecularity of the products is a function of steric bulk with monodentate ligands and a function of chelate bite with bidentate ligands. The geometry of the products is controlled largely by the trans influence of both neutral and anionic groups. Where the steric constraints involved in nucleophilic attack of the complexes by bulky ligands are dominant, olefin displacement can be prevented entirely. Reactions of [PtXYL2] (X = Y = Ph, Cl; X = Ph, Y = Cl; L = monodentate ligand, L2 = bidentate ligand) with carbon monoxide have been studied by 31P{1H} and 13C{1H} NMR and infrared spectroscopies. The mechanism of carbonyl insertion at platinum(II) is discussed in terms of the chelate effect and the trans influence of the anionic ligands.
Reactivity of platinum diolefin complexes. Roles of trans influence and chelate effect
Anderson,Clark,Davies
, p. 1636 - 1639 (2008/10/08)
The complex [PtCl2(cod)] (cod = 1,5-cyclooctadiene) reacts with CO and tertiary phosphine to produce cis-[PtCl2(CO)L] (L = PEt3, P-n-Bu3, PMePh2, PPh3, P(C6H4F-p)
