Carbon monoxide labilization and hydrogen-transfer pathways in cationic phosphido-bridged rhenium-platinum heterobimetallic systems and the molecular structures of [.eta.5-Cp(ON)Re(.mu.-PR2)(.mu.-H)Pt(PPh3)2]X (R = Cy, X- = PF6-; R = Ph, X- = BF4) and [.eta.5-Cp(ON)HRe(.mu.-PCy2)Pt(PPh3)2]BF4, a rare example of bridging- and terminal-hydrido geometric isomers

Powell, John Wesley; Sawyer, J. F.; Stainer, Matthew

doi:10.1021/ic00324a009

Inorg. Chem.

1989

DOI: 10.1021/ic00324a009

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Carbon monoxide labilization and hydrogen-transfer pathways in cationic phosphido-bridged rhenium-platinum heterobimetallic systems and the molecular structures of [.eta.5-Cp(ON)Re(.mu.-PR2)(.mu.-H)Pt(PPh3)2]X (R = Cy, X- = PF6-; R = Ph, X- = BF4) and [.eta.5-Cp(ON)HRe(.mu.-PCy2)Pt(PPh3)2]BF4, a rare example of bridging- and terminal-hydrido geometric isomers

John Wesley Powell¹,

J. F. Sawyer²,

Matthew Stainer³

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Cited by 32 publications

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Synthesis and Structure of Heterobimetallic Compounds with a Single Thiolato-Bridged Ligand

Hossain¹,

Lin²,

Shyu³

2001

Eur. J. Inorg. Chem.

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Keywords: Tungsten / Molybdenum / S ligands / Bridging ligands Reactions between CpFe(CO) 2 SPh and M(CO) 5 THF (M = Cr, Mo, and W) in a mixture of benzene and THF at room temperature afforded compounds of the type CpFe(CO) 2 (µ-SPh)M(CO) 5 (1) [M = Cr (1a), Mo (1b), and W (1c)] in high yield. However, migration of the thiolato ligand occurred during reactions between CpM(CO) x SPh (M = Fe, x = 2; M = Mo and W, x = 3) and Fe 2 (CO) 9 forming compounds [Fe(µ-SPh)(CO) 3 ] 2 and [CpM(CO) x ] 2 (M = Fe, x = 2; M = Mo and

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Synthesis and Structure of Heterobimetallic Compounds with a Single Thiolato-Bridged Ligand

Hossain¹,

Lin²,

Shyu³

2001

Eur. J. Inorg. Chem.

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Regiospecific Reaction between Dimetallic Phosphido-Bridged W−W Complexes and Phosphane Imide − Electrophilic Site Switching by Metal−Metal Bond Formation

Shyu¹,

Singh²,

Su³

et al. 2002

Eur. J. Inorg. Chem.

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Reaction between CpW(CO)2(μ‐PPh2)W(CO)5(W−W) (2) and Ph3P=NR (R = Pr, CH2Ph, iPr) in THF at refluxing temperature is regiospecific with the CNR ligand coordinated to the W(CO)4 unit to produce CpW(CO)2(μ‐PPh2)W(CO)4(CNR)(W−W) (4). Spectroscopic data indicate that the complex exists in two stereoisomeric forms in solution. The structure of the cis isomer was determined by a single‐crystal X‐ray diffraction study which indicates that the CNR ligand is coordinated to the W atom of the W(CO)4 unit and cis to the phosphido bridge. Reaction between CpW(CO)3(μ‐PPh2)W(CO)5 (1) and Ph3P=NR (R = Pr, CH2Ph, iPr) in THF under similar condition is also regiospecific. However, the CNR ligand is coordinated to the CpW site to produce CpW(CO)2(CNR)(μ‐PPh2)W(CO)5 (3). There are also two stereoisomers of the complex, which were separated by column chromatography. Structures of both isomers were determined by single‐crystal X‐ray diffraction studies. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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ChemInform Abstract: CO Labilization and Hydrogen‐Transfer Pathways in Cationic Phosphido‐Bridged Re‐Pt Heterobimetallic Systems and the Molecular Structures of (η5‐Cp(ON)Re(μ‐PR2)(μ‐H)Pt(PPh3)2)X (R: Cy, X‐: PF‐ 6; R: Ph, X‐: BF‐ 4) and Cyclic (η5‐Cp(ON)HRe(μ‐PCy2)Pt(PPh3)2)BF4, a Rare Example of Bridging‐ and Terminal‐Hydrido Geometric Isomers.

1990

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ChemInform Abstract The reaction of the cationic sec. phosphine complexes (I) with Pt(PPh3)4 (II) leads to CO loss and the formation of the terminal Re hydride derivative (III) ((IIIb): space group P21/n, Z=4) as the kinetic product. On standing, (III) slowly transforms into the thermodynamically preferred bridging-hydrido isomer (IV) ((IVa), (IVb): for both P1, Z=2). However, the oxidative addition of (Ib) and (Ic) to the ethylene-Pt(II) complex (V) gives the complexes (VI). The cations (VI) will undergo slow CO loss to form (III) in the presence of base and the isomerization of (III) to (IV) is promoted by added chloride ion. The mechanism of formation of (III) and (VI) from (I) and the mechanism of the base-promoted (VI) to (III) rearrangement and the Cl-catalyzed (III) to (IV) isomerization process are discussed.

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Cited by 32 publications

References 2 publications

Synthesis and Structure of Heterobimetallic Compounds with a Single Thiolato-Bridged Ligand

Synthesis and Structure of Heterobimetallic Compounds with a Single Thiolato-Bridged Ligand

Regiospecific Reaction between Dimetallic Phosphido-Bridged W−W Complexes and Phosphane Imide − Electrophilic Site Switching by Metal−Metal Bond Formation

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