82822-31-9

Upstream product

• 21264-32-4 diacetonitriledichloridopalladium(II) 
• 62144-65-4 1,2-bis((diphenylphosphino)methyl)benzene 
• 14056-88-3 trans-dichlorobis(triphenylphosphine)platinum(II) 
• 10199-34-5 cis-dichlorobis(triphenylphosphine)platinum(II) 
• 12080-32-9 dichloro( 1,5-cyclooctadiene)platinum(ll) 
• 10025-99-7 potassium tetrachloroplatinate(II) 

Downstream Products

• 132779-78-3 (1,2-bis{(diphenylphosphino)methyl}benzene)dibromoplatinum(II) 
• 132779-80-7 (acrylonitrile)(1,2-bis{(diphenylphosphino)methyl}benzene)platinum(II) 
• 128480-55-7 (1,2-bis{(diphenylphosphino)methyl}benzene)(ethene)platinum(II) 
• 1359746-78-3 (1,1-dicyanoethylene-2,2-dithiolate)Pt(1,2-C₆H₄(CH₂PCy₂)2) 
• 1027104-99-9 [Pt(SH)2(o-bis(diphenylphosphinomethyl)benzene)] 
• 132779-79-4 (1,2-bis{(diphenylphosphino)methyl}benzene)diiodoplatinum(II) 

Relevant academic research and scientific papers

Synthesis and characterisation of 2,2-bis(hydroxymethyl)-1,3-diselenolato metal(II) complexes bearing various phosphanes

An improved synthesis of 4,4-bis(hydroxymethyl)-1,2-diselenolane and the complexation properties of the corresponding diselenolato dianion to group-10 metals are reported. We describe an efficient and straightforward procedure that bypasses the isolation of the malodorous and airsensitive diselenol and starts with the diselenide appropriate group-10 metal complex bearing phosphane and chlorido ligands. A series of complexes with various monoand bidentate phosphanes is prepared and characterised by multinuclear NMR spectroscopy, mass spectrometry, and elemental analysis. Furthermore, the structure of most complexes is studied by single-crystal X-ray diffraction to establish their supramolecular arrangement in the solid state. Consequently, several group-10 metal complexes with P-M-P angles (bite angles) in the range from 71-108° are investigated. The use of the sterically demanding bridging phosphane 4,5-bis(diphenylphosphanyl)-9,9-dimethylxanthene, which exhibits a large bite angle yields a mixture of a di- and trinuclear complex. While the platinum-containing complexes are proven to be rather stable, the palladium and nickel analogues tend to decompose. Especially, the nickel complexes were found to be sensitive against: oxidation. This circumstance leads to the formation of the so far unknown 1,8-bis(diphenylphosphanyl)naphthalene monooxide, the formation and structure of which could be confirmed from NMR spectroscopic data and single-crystal X-ray diffraction.

Palladium complexes of the heterodiphosphine o- C6H 4(CH2PtBu2)(CH2PPh 2) are highly selective and robust catalysts for the hydromethoxycarbonylation of ethene

The coordination chemistry and ethene hydromethoxycarbonylation catalysis with the diphosphine o-C6H4(CH2P tBu2)(CH2PPh2) (L3) is reported and the results compared with the analogous chemistry of the symmetrical diphosphines o-C6H4(CH2P tBu2)2 (L1) and o-C 6H4(CH2PPh2)2 (L 2). Palladium-catalyzed ethene hydromethoxycarbonylation studies under the commercial catalytic conditions are reported. The results obtained using L1-3 as supporting ligands show that the catalysts derived from L3 and L1 have similar activity and selectivity for methyl propanoate (MeP). In addition, the Pd-L3 catalyst has much greater longevity than the Pd-L1 catalyst. Treatment of the appropriate [Pt(X)(Y)(cod)] with L3 gave [PtCl2(L 3)] (3), [Pt(CH3)2(L3)] (6), and [PtCl(CH3)(L3)] (9). At equilibrium, complex 9 is a 90:1 mixture of geometric isomers 9a (with CH3 trans to the tBu2P) and 9b (with Cl trans to the tBu 2P). The fluxionality of complex 3, detected by 1H NMR, is interpreted in terms of the conformation of the seven-membered chelate. The complexes [Pt(CH3)(PMe3)(L3)]Cl (10b) and [PtH(PPh3)(L3)]Cl (12b) are formed as essentially single isomers with CH3/H trans to the Ph2P group. The palladium complexes [PdCl2(L3)] (13), [PdCl(CH3)(L 3)] (14a/14b), and [PdH(PCy3)(L3)]BF 4 (15b) have been made by similar methods to their platinum analogues. The factors controlling the relative isomer stabilities are explored experimentally and computationally. The complexes [PtCl2(L 4)] (16) and [PtCl(CH3)(L4)] (17a/17b) where L4 = o-C6H4(CH2PnBu 2)(CH2PPh2) are reported, and the geometric isomers of 17 are almost isoenergetic. The crystal structures of 3, 14a, 15b, and 16 have been determined by X-ray crystallography. DFT calculations on complexes of the type [Pt(X)(Y)(L3)] gave only small calculated differences in energy between the geometrical isomers (0-4 kcal mol -1), which are consistent with the experimental observations. It is suggested that repulsive intramolecular HAAAH interactions (between the Pt-CH3 and PC(CH3)3 groups) determine which isomer predominates. The reasons for the favorable catalytic properties of the Pd-L3 catalyst are probed by 13CO reactions with the model complexes 9a/9b and 14a/14b, and the structures of the resulting acyl complexes are assigned on the basis of 13C and 31P NMR and IR spectroscopy. From these studies, it is suggested that the reason for the Pd-L3 catalyst resembling the Pd-L1 catalyst in terms of selectivity is that the crucial acyl intermediates are similar.

Synthesis spectroscopic and structural properties of transition metal complexes of the o-xylyl diphosphine o-C6H4(CH 2PPh2)2

The systematic coordination chemistry of the wide-angle diphosphine o-C6H4(CH2PPh2)2 (L 1) has been investigated with metal ions from Groups 9-11 in order to explore the consequences of the steric demands of the phosphine and its flexibility towards different oxidation states and coordination geometries. The products isolated include the tetrahedral [CoX2(L1)] (X = Cl, Br or I), the very distorted square planar [Rh(L1) 2]+, [M(cod)(L1)]+ (M = Rh or Ir), square planar [NiX2(L1)] (X = Cl or Br), [M′Cl 2(L1)] (M′ = Pd or Pt), the chloro-bridged [Pd 2Cl2(L1)2]2+, [Pd(L 1)2]2+, the tetrahedral [M″(L 1)2]+ (M″ = Cu, Ag or Au) and the dinuclear [(AuCl)2(L1)]. Chemical oxidation of some of the complexes are described, giving examples of Co(III), Ni(III) and Pt(IV) species. Where possible the products have been characterised by IR, UV-vis, NMR (1H, 31P, 63Cu and 195Pt as appropriate) spectroscopies, mass spectrometry and microanalysis. Crystal structures of six representative examples confirm the coordination environments in particular species and illustrate the steric demands of L1. L 1 is a versatile ligand which can readily alter its chelate bite angle to accommodate a range of coordination geometries (the P?P distances within the chelate rings varies by >0.5 ?), and the presence of the rigid aromatic ring in the C4 backbone leads to some preorganisation favouring cis chelation. It also shows a preference for low coordination numbers and this results in some unexpected products.

209. The Coordination Chemistry of 1,2-Bisbenzene with Nickel(II), Palladium(II), Platinum(II), and Platinum(0) and the X-Ray Crystals Structure of benzene)(C2H4)>

The preparation of complexes (M = Ni, Pd, and Pt; X = Cl, Br, and I; 1 = 1,2-bisbenzene), , (alkene = C2H4 and CH2 = CHCN), and is reported.Their 1H- and 31P-NMR spectra were recorded and used for structural assignments.The X-ray crystal structure of was determined.It is shown that the P-Pt-P bond angle in this complex differs significantly from those found in related compounds with monodentate phosphines, and that this difference is likely to be due to intramolecular contacts.