Formation of Diphenylphosphanylbutadienyl Complexes by Insertion of Two P-Coordinated Alkynylphosphanes into a PtbC6F5 Bond: Detection of Intermediate and Reaction Products

Platinum complexes having redox-active PPh2CCFc and/or CCFc as terminal or bridging ligands

“…8,10-12,39-41,44,86, 92 The P-C a , C a ∫C b bond lengths and the angles P-C a -C b , C a -C b -Cg are also comparable to those observed in related platinum complexes. The two cis-alkynylphosphine entities in the complex 1 are found staggered, with a torsional angle C a -P a -P b -C a ¢ of 65.0(3) 39 It should be noted that the separation between the C a atoms, which has been related to the ease of acetylenic units coupling, is 3.303(9) A ˚. This value is comparable to those found in [cis-Pt(R F ) 2 (PPh 2 C∫CPh) 2 ] (3.20(2) A ˚) and [cis-Pt(R F ) 2 (PPh 2 C∫CTol) 2 ] (3.34(2) A ˚), 39 which undergo intramolecular coupling of both alkynylphosphine ligands.…”

“…The two cis-alkynylphosphine entities in the complex 1 are found staggered, with a torsional angle C a -P a -P b -C a ¢ of 65.0(3) 39 It should be noted that the separation between the C a atoms, which has been related to the ease of acetylenic units coupling, is 3.303(9) A ˚. This value is comparable to those found in [cis-Pt(R F ) 2 (PPh 2 C∫CPh) 2 ] (3.20(2) A ˚) and [cis-Pt(R F ) 2 (PPh 2 C∫CTol) 2 ] (3.34(2) A ˚), 39 which undergo intramolecular coupling of both alkynylphosphine ligands. 44 In complex 1, the cis-disposition allows the presence of p ◊ ◊ ◊ p contacts involving the C 6 F 5 ligands and the C(7-12) and C (31)(32)(33)(34)(35)(36) phenyl rings, (3.258(8) A ˚, 3.118(9) A ˚, interplanar angles 13.3(3) • , 21.0(2) • ; Fig.…”

“…Thus, interesting m-2,3-bis(diphenylphosphino)-1,3-butadien-1yl, diphosphine bridging {m-C(R)=C(PPh 2 )C(PPh 2 )=C(R)(R F )} and {m-C(R F )=C(PPh 2 )C(PPh 2 )=C(R) 2 } complexes are accessible from initial bis(h 2 -alkyne) adducts [m-kP:h 2 -(PPh 2 C∫CR) 2 ] by sequential insertion of two PPh 2 C∫CR into a Pt-C 6 F 5 bond. 10,38, 39 Furthermore, bis(phosphino)naphthalene moieties and/or chelating 1,2-diphosphinoalk-1-ene complexes were obtained by thermolysis or photolysis of [cis-Pt(C 6 F 5 ) 2 (PPh 2 C∫CR) 2 ] through a [2 + 2 + 2] cycloaddition or activation of a P-C(Ph) bond, respectively. 44 Departamento de Química-Grupo de Síntesis Química de La Rioja, UA-CSIC, Universidad de La Rioja, 26006, Logroño, Spain.…”

Alkynylphosphanes as supports for mixed-metal Co4M (M=Ru, Os) fluoride complexes: Syntheses, structures and thermolysis studies

“…The application of alkynylphosphanes (PR 2 C"CR, R = hydrocarbyl) in organometallic chemistry has been the subject of considerable research activities over the last three decades which can, in part, be attributed to their polyfunctional nature [1,2] and also to their capacity to undergo coupling/insertion reactions with other coordinated groups [3][4][5][6][7]. These coupling reactions can occur with the intact ligand [3,4] or with units derived from fragmentation of the alkynylphosphane (e.g., phosphide and acetylide) [5][6][7].…”

“…These coupling reactions can occur with the intact ligand [3,4] or with units derived from fragmentation of the alkynylphosphane (e.g., phosphide and acetylide) [5][6][7]. In addition, their use to promote the formation of homoand hetero-metallic clusters has been documented [8].…”