15094-61-8Relevant academic research and scientific papers
Comparative time-resolved IR and UV spectroscopic study of monophosphine and diphosphine platinum (II) azido complexes
Hennig, Horst,Ritter, Klaus,Chibisov, Alexander K.,G?rner, Helmut,Grevels, Friedrich-Wilhelm,Kerpen, Klaus,Schaffner, Kurt
, p. 160 - 166 (2008/10/08)
Solutions of cis-diazido-bis(triphenylphosphine)platinum(II) (cis-[PtII(PPh3)2(N3)2]) and diazido-1,3-bis(diphenylphosphino)-propaneplatinum(II) ([PtII(dppp) (N3)2]) w
Electrochemical studies on metal derivatives of buckminsterfullerene (C60)
Lerke, Susan A.,Parkinson,Evans, Dennis H.,Fagan, Paul J.
, p. 7807 - 7813 (2007/10/02)
The electrochemical properties of the complexes (Ph3P)2Pt(η2-C60), (Et3P)2M(η2-C60), [(Et3P)2M]C60 (M = Ni, Pd, Pt; Et - ethyl, Ph - phenyl), and [(Et3P)2Pt]nC60 (n = 2-4) have been investigated. In the case of the monosubstituted complexes (Ph3P)2Pt(η2-C60) and (Et3P)2M(η2-C60), three to four sequential one-electron reduction waves are observed shifted to more negative potentials relative to C60. Reduction is accompanied by loss of the metal fragment (R3P)2M. The rate of metal dissociation upon reduction is dependent on the identity of the phosphine ligand ((Ph3P)2Pt(η2-C60)2- > (Et3P)2Pt(η2-C60)2-), the metal (Ni > Pd > Pt), and the extent of reduction ((Et3P)2PtC603- > (Et3P)2PtC602- > (Et3P)2PtC60-). The cyclic voltammograms have been simulated to obtain kinetic and thermodynamic information regarding these processes. The reduction events in the metal complexes are C60-centered, whereas the irreversible oxidation waves observed for these complexes are proposed to be metal-centered from comparison with the model complexes (Et3P)2M(η2-CH2=CHCO 2CH3) (M = Ni, Pd, Pt). The results lead to the conclusion that there is negligible extension of d-orbital backbonding density beyond the carbon-carbon double bond where the metal is attached. Coordination of one of these metals to C60 is proposed to lower the electron affinity of the carbon cluster by effectively removing one of the C60 carbon-carbon double bonds from conjugation and inductively adding electron density to the a bond framework. Addition of more metals continues to lower the electron affinity of the C60 core, with the reversible potentials for [(Et3P)2Pt]nC60 shifting 0.36 V in the negative direction with each metal added for n = 0-4.
Electrophilic Behaviour of Dicarbonylbis(pentamethylcyclopentadienyl)-dirhodium towards Diazoalkanes and Low-valent Platinum Compounds: X-Ray Crystal Structure of
Green, Michael,Mills, Rona M.,Pain, Geoffrey N.,Stone, F. Gordon A.,Woodward, Peter
, p. 1309 - 1320 (2007/10/02)
The diazoalkanes R1R2CN2 react with the dirhodium compound to give the complexes 1R2)(CO)2(η-C5Me5)2> (R1=R2=H or CF3; R1=H, R2=CO2Et; R1=H, R2=CH=CH2), the i.r and n.m.r. data for which are reported and discussed.The dirhodiumplatinum compounds (cod=cyclo-octa-1,5-diene), , and have been isolated from reactions between low-valent platinum species and or .Spectroscopic properties are reported which are in accord with molecular structures in which PtL2 fragments are 'complexed' with a molecule giving rise to a PtRh2 triangle semi-triply bridged by two CO ligands.This has been confirmed by an X-ray diffraction study on 3-CO)2(CO)(PPh3)(η-C5Me5)2>, crystals of which are triclinic, space group P1, in a unit cell with a=11.185(3), b=13.278(7), c=15.443(9) Angstroem, α=102.98(5), β=92.18(4), γ=105.88(4) deg, and Z=2.The structure was solved to R 0.056 (R' 0.058) from 4 285 observable independent reflections =3.0?(I)> collected at 220 K in the range 2Θa triangle of metal atoms .The platinum atom is in a planar environment with respect to the two rhodium atoms and the CO and the PPh3 ligands to which it is terminally bound.The longer Pt-Rh bond is essentially trans to CO.On either face of the metal triangle two other CO ligands bridge the Rh-Rh bond and lean towards the platinum in a semi-triply bridging manner .Each rhodium is η5-co-ordinated to a C5Me5 group, as expected.The reaction between and affords the thermally unstable and air sensitive complex , while the salt has been prepared from and .The i.r and n.m.r. data for these species are discussed.
