62922-35-4

Upstream product

• 7647-01-0 hydrogenchloride 
• 59765-06-9 bis(di-t-butylphenylphosphine)platinum⁽⁰⁾ 
• 106819-57-2 PtHCl(CO)(P(C(CH₃)3)2C₆H₅) 
• 106763-09-1 Pt₂Cl₂(CO)2(P(C(CH₃)3)2C₆H₅)2 
• 106763-08-0 PtHCl(CO)(P(C(CH₃)3)2C₆H₅) 
• 62931-81-1 Pt3(μCO)3(P-tert.-Bu2Ph)3 
• 73889-59-5 trans-{di-tert-butylphenylphosphine}2-platinum(II)Cl₂ 
• 64997-13-3 1,2-dibromocyclohept-1-ene 

Relevant academic research and scientific papers

Cyclohexyneplatinum(0) Complexes Containing Di-t-butylphenylphosphine, t-Butyldiphenylphosphine or Trimethylphosphine

Cyclohexyneplatinum(0) complexes Pt(C6H8)L2 (L = PBut2Ph (4), PButPh2 (5)> analogous to the known complex (3) (L = PPh3) have been prepared by reaction of the two-coordinate complexes PtL2 with 1,2-dibromocyclohexene and 1percent sodium amalgam.The corresponding tricyclohexylphosphine complex is formed by a similar reaction but it could not be isolated in a pure state.Attempts to prepare analogues of (4) and (5) containing cycloheptyne or cyclooctyne were unsuccessful, possibly because the bulky t-butyl groups of the tertiary phosphines hinder coordination of the largerrings.Bulky tertiary phosphines do not displace PPh3 from (3) but trimethylphosphine reacts with (3) to give successively Pt(C6H8)(PMe3)(PPh3) (10) and Pt(C6H8)(PMe3)2 (11), as shown by 31P n.m.r spectroscopy.The tertiary phosphines in these complexes equilibrate rapidly at room temperature in benzene and only (10) can be isolated as a solid from the reaction.Complexes (4) and (5) react with HCl (1 molar proportion) to give η1-cyclohexen-1-yl complexes trans-PtCl(C6H9)L2 t2Ph (6), PButPh2 (7)>.In the absence of air, (4) reacts with methanol at 65 deg C to give the hydrido complex trans-PtH(C6H9)(PBut2Ph)2 (8).In the presence of oxygen from the air, however, the main product is the dioxygen complex Pt(O2)(PBut2Ph)2 (9).This represents an unusual example of complete displacement of cyclohexyne from a platinum(0) complex by a ?-acceptor ligand.

Reaction of Pt3(CO)3(P-t-Bu2Ph)3 and HCI. The x-ray structure of Pt2Cl2(CO)2(P-t-Bu2Ph)2

The reaction of Pt3(CO)3(P-t-Bu2Ph)3 (1) with 3 equiv of HCl at -50°C results in immediate formation of PtHCl(CO)(P-t-Bu2Ph) (2) in which the hydride ligand is assigned to the position trans to the CO ligand. Complex 2 isomerizes rapidly at higher temperatures to give a second complex, PtHCl(CO)(P-t-Bu2Ph) (3), with the hydride ligand trans to the chloride ligand. Complex 3 slowly converts to a dinuclear Pt(I) complex shown by X-ray crystallography to be Pt2Cl2(CO)2(P-t-Bu2Ph)2 (4). Complex 4 crystallizes in the monoclinic space group P21/c with Z = 4 in a unit cell of dimensions a = 15.418 (1) A?, b = 14.751 (1) A?, c = 16.051 (2) A?, and β = 108.61 (1)°. The structure was refined by using 4065 independent reflections with 203 variables to R1 = 0.046 and R2 = 0.053. 4 contains an unsupported Pt-Pt bond (2.628 (1) A?), and the phosphine ligands are located trans to this bond. The Pt atom coordination spheres are essentially square-planar with a dihedral angle of 109.9° between the two planes. The rotational energy of the Pt-Pt bond and the relative stability of 4 and a hypothetical Cl-bridged isomer are examined by using EHMO calculations. 4 also can be prepared by reacting 1.5 equiv of Cl2 with 1 while reaction of 1 or 4 with excess Cl2 gives Pt(Cl)2(CO)(P-t-Bu2Ph) (7). Addition of excess NaBH4 to a solution of 3 regenerates 1, and reaction of 3 with AgPF6 gives [(Pt3(μ-CO)3(P-t-Bu2Ph)3) 2Ag] [PF6] (6). Complex 6 has been spectroscopically characterized as a Ag cation sandwiched between two units of 1. 6 is also the product of the reaction of 1 and AgPF6.