Binuclear molybdenum carbonyls bridged both by hydride and bidentate phosphine ligands. Crystal and molecular structures of salts of hydridomolybdenum carbonyls with bidentate phosphine ligands (.mu.-H)(.mu.-Ph2P(CH2)nPPh2)Mo2(CO)8- (n = 1-4) and their reactions with acids

1984 ◽  
Vol 106 (9) ◽  
pp. 2583-2591 ◽  
Author(s):  
Marcetta Y. Darensbourg ◽  
Ramadan El Mehdawi ◽  
Terry J. Delord ◽  
Frank R. Fronczek ◽  
Steven F. Watkins
Keyword(s):  
Phosphine Ligands ◽  
Molecular Structures ◽  
Crystal And Molecular Structures ◽  
Bidentate Phosphine ◽  
Molybdenum Carbonyls

The Reaction of (PPri3)2H2Cl2Ir With Phosphines: Crystal and Molecular Structures of mer-cis-(PMe2Ph)2(PPri3)-cis-Cl2HIrIII and mer-cis-(PMe2Ph)2(PPri3)-trans-Cl2HIrIII

1993 ◽  
Vol 46 (4) ◽  
pp. 529 ◽  
Author(s):  
EJ Ditzel ◽  
GB Robertson
Keyword(s):  
Phosphine Ligands ◽  
Molecular Structures ◽  
Iridium Complex ◽  
Steric Strain ◽  
Distorted Octahedral Coordination ◽  
Crystal And Molecular Structures ◽  
Distorted Octahedral ◽  
Spontaneous Reaction ◽  
Summary Data ◽  
Metal Ligand

Ambient temperature reactions of the complex (PPri3)2H2Cl2IrIV (1) with ethyl-substituted monodentate phosphine ligands are shown to yield different product types to those obtained both with methyl-substituted analogues and with phosphine itself. With the phosphines PH3 and PMe3-nPhn (n = 0, 1) there is spontaneous reaction to give the complexes mer-trans-(Ppri3)2(PR3)H-trans-Cl2IrIII, whereas with PEt3-nPhn (n = 0-2) the reaction yields mer-cis-(PR3)2(PPri3)H-trans-Cl2IrIII complexes. Under reflux the phosphines PMe3 and PMe2Ph also yield mer-cis-(PR3)2(PPri3)H-trans-Cl2IrIII complexes [PR3 = PMe3 (2), Pme2Ph (3)]. The differing course of the reactions of (1) with PMe3 and with PEt3 has permitted the synthesis of mer-(Pme3)-trans-(PPri3)(PEt3)H-trans-Cl2IrIII, the first example of an octahedral iridium complex containing three different monodentate phosphine ligands. All of the products obtained have been fully characterized by 31P and 1H n.m.r. spectroscopy. Crystal structure analyses of (3) and of its photoisomer mer-cis-(PMe2Ph)2(PPri3)H-cis-Cl2IrIII (4) have been carried out to permit comparison of the metal-ligand bonding in these complexes with that in their previously characterized, sterically less crowded, tris-PMe2Ph analogues. Summary data are as follows: (3), triclinic, Pī, a 13.414(1), b 12.062(1), c 9.077(1) Ǻ, α 79.53(1), β 88.05(1), γ 79.47(1)° [T 158�3 K], Z 2, R 0.022, Rw 0.032 (4822 reflections); (4), monoclinic, P21/n, a 19.694(1), b 15.972(1), c 9.548(1) Ǻ, β 101.45(1)° (T 293�2 K), Z 4, R 0.026, Rw 0.032 (5476 reflections). Both molecules exhibit distorted octahedral coordination of the metal atom and appreciably greater steric strain than in their (Pme2Ph)3HCl2IrIII analogues. Metal-ligand distances to the mutually trans Pme2Ph and PPri3 ligands are 2.322(1) and 2.372(1)Ǻ, respectively, for (3), and 2.359(1) and 2.406(1)Ǻ for (4), and suggest that the thermodynamically favoured cis-dichloro isomer (4) is the more strained. The preparations of the complexes (PCy3)2H2Cl2IrIV (1a) and (PCy3)2H2Br2IrIV (1b) (Cy = cyclohexyl), and their reactions with the same phosphines as used with (1), are also reported.

Reactions of RuCl(C=CHBut)(PPh3)(hC5Me5) with Tertiary Phosphites: Molecular Structure of RuCl{P(OPh)3} 2(h;-C5Me5)

1997 ◽  
Vol 50 (11) ◽  
pp. 1097 ◽  
Author(s):  
Michael I. Bruce ◽  
Ben C. Hall ◽  
Edward R. T. Tiekink
Keyword(s):  
Molecular Structure ◽  
Phosphine Ligands ◽  
Molecular Structures ◽  
Tertiary Phosphine ◽  
Crystal And Molecular Structures

Reactions between RuCl(C=CHBut)(PPh3)(η-C5Me5) and tertiary phosphites result in displacement of both vinylidene and tertiary phosphine ligands to give RuCl{P(OR)3}2(η-C5Me5) (R = Me, Ph). The crystal and molecular structures of RuCl{P(OPh)3}2(η-C5Me5) are reported.

New adducts of silver(I) halides, AgX (X = Cl, Br), with bidentate phosphine ligands: syntheses and molecular structures of [Ag3(μ3-Cl)2(μ-dppm)3][PF6], [Ag3(μ3-Br)2(μ-dppm)3][AgBr2], {[Et4N][Ag2 (μ-Br)3(μ-dppe)]}n, [Et4N]2[(AgCl2)2(μ-dppe)], and [(AgCl)2(μ-dppp)2]

2017 ◽  
Vol 72 (5) ◽  
pp. 327-334
Author(s):  
Ting-Ting Qian ◽  
Yu-Feng Xie ◽  
Hua-Tian Shi ◽  
Ai-Quan Jia ◽  
Qian-Feng Zhang
Keyword(s):  
Membered Ring ◽  
Phosphine Ligands ◽  
Molecular Structures ◽  
Anionic Complex ◽  
Polymeric Complex ◽  
X Ray Diffraction ◽  
Neutral Complex ◽  
X Ray ◽  
Trigonal Bipyramidal ◽  
Bidentate Phosphine

AbstractInteraction of AgCl with bis(diphenylphosphino)methane (dppm) in THF/MeCN in the presence of K[PF6] or [Et4N]Br afforded typical trinuclear cationic trigonal-bipyramidal complexes [Ag3(μ3-Cl)2(μ-dppm)3][PF6] (1) or [Ag3(μ3-Br)2(μ-dppm)3][AgBr2] (2), respectively. Treatment of AgBr with bis(diphenylphosphino)ethane (dppe) in THF/MeCN in the presence of [Et4N]Br gave a polymeric complex {[Et4N][Ag2(μ-Br)3(μ-dppe)]}n (3) with a dinuclear {Ag2(μ-Br)3} core. The reaction of AgCl with dppe or bis(diphenylphosphino)propane (dppp) in THF/MeCN in the presence of [Et4N]Cl resulted in the isolation of a dinuclear anionic complex [Et4N]2[(AgCl2)2(μ-dppe)] (4) with one μ-dppe bridge or a dinuclear neutral complex [(AgCl)2(μ-dppp)2] (5) with two μ-dppp bridges and a 12-membered ring, respectively. The structures of complexes 1–5 with the bidentate phosphine ligands were determined by single-crystal X-ray diffraction.

A Solvent-Dependent and Electrochemically Controlled Self-Assembling/Disassembling System

2003 ◽  
Vol 68 (9) ◽  
pp. 1647-1662 ◽  
Author(s):  
Valeria Amendola ◽  
Massimo Boiocchi ◽  
Yuri Diaz Fernandez ◽  
Carlo Mangano ◽  
Piersandro Pallavicini
Keyword(s):  
Equilibrium Mixture ◽  
Bidentate Ligand ◽  
Molecular Structures ◽  
The Self ◽  
Molar Ratio ◽  
Crystal And Molecular Structures ◽  
Self Assembling ◽  
Irreversible Oxidation ◽  
Irreversible Reduction ◽  
Metal Ligand

The bis-bidentate ligand R,S-1,2-diphenyl-N,N'-bis(2-quinolinemethylidene)ethane-1,2-diamine (ligand 4), containing two (iminomethyl)quinoline moieties separated by a cis-1,2-diphenylethylene spacer, forms stable complexes with both CuI and CuII. With CuII, the monomeric 1:1 complex [CuII(4)]2+ is obtained both in CH3CN and CH2Cl2. With CuI and overall 1:1 metal/ligand molar ratio, an equilibrium mixture is obtained in CH3CN, consisting of [CuI(4)2]+, [CuI2(4)2]2+ and [CuI2(4)(CH3CN)4]2+. The preponderant species is the two-metal one-ligand "open" complex [CuI2(4)(CH3CN)4]2+, in which each Cu+ cation is coordinated in a tetrahedral fashion by one (iminomethyl)quinoline unit and by two CH3CN molecules. Precipitation from the equilibrium mixture yields only crystals of [CuI2(4)(CH3CN)4](ClO4)2·2CH3CN, whose crystal and molecular structures have been determined. On the other hand, in the poorly coordinating CH2Cl2 solvent, only the dimeric helical [CuI2(4)2]2+ complex is obtained, when the overall metal/ligand 1:1 molar ratio is chosen. Addition of large quantities of acetonitrile to solutions of [CuI2(4)2]2+ in dichlorometane results in the formation of [CuI2(4)(CH3CN)4]2+, i.e. in the solvent-driven disassembling of the CuI helicate. While electrochemistry in CH3CN is poorly defined due to the presence of more than one CuI species, cyclic voltammetry experiments carried out in CH2Cl2 revealed a well defined behavior, with irreversible oxidation of [CuI2(4)2]2+ and irreversible reduction of [CuII(4)]2+ taking place at separate potentials (∆E ≈ 700 mV). Irreversibility and separation of the redox events are due to the self-assembling and disassembling processes following the reduction and oxidation, respectively.

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