Oxidatively enhanced intramolecular carbonyl scrambling in the mixed-metal cluster [Re7C(CO)21Rh(CO)2]2-

Simerly, Scott W.; Shapley, John R.

doi:10.1021/ic00344a003

Cited by 7 publications

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“…The synthesis of a number of mixed-metal clusters involving rhenium has been effected by utilizing the cluster [Re 7 C(CO) 21 ] 3- , as a pseudo-Cp ligand to react with metal complex electrophiles . A variety of stable heterometallic derivatives [Re 7 C(CO) 21 ML n ] 2- , where M = Cu, Ag, Au , Pd, , Pt, Hg, Rh, , and Ir, , have been reported. In contrast, the related octahedral cluster compound [Re 6 C(CO) 19 ] 2- 10,11 apparently forms only weak complexes with copper triad electrophiles .…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Comparative Properties of [PPN]₂[Re₆C(CO)₁₈Mo(CO)₄] and [PPN]₂[Re₆C(CO)₁₈Ru(CO)₃]

1996

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The reaction of [PPN](2)[Re(6)C(CO)(19)] with Mo(CO)(6) and Ru(3)(CO)(12) under sunlamp irradiation provided the new mixed-metal clusters [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] and [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)], which were isolated in yields of 85% and 61%, respectively. The compound [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] crystallizes in the monoclinic space group P2(1)/c with a = 20.190 (7) Å, b = 16.489 (7) Å, c = 27.778 (7) Å, beta = 101.48 (2) degrees, and Z = 4 (at T = -75 degrees C). The cluster anion is composed of a Re(6)C octahedral core with a face capped by a Mo(CO)(4) fragment. There are three terminal carbonyl ligands coordinated to each rhenium atom. The four carbonyl ligands on the molybdenum center are essentially terminal, with one pair of carbonyl ligands (C72-O72 and C74-O74) subtending a relatively large angle at molybdenum (C72-Mo-C74 = 147.2(9) degrees ), whereas the remaining pair of carbonyl ligands (C71-O71 and C73-O73) subtend a much smaller angle (C71-Mo-C73 = 100.5(9) degrees ). The (13)C NMR spectrum of (13)CO-enriched [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] shows signals for four sets of carbonyl ligands at -40 degrees C, consistent with the solid state structure, but the carbonyl ligands undergo complete scrambling at ambient temperature. The (13)C NMR spectrum of (13)CO-enriched [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)] at 20 degrees C is consistent with the expected structure of an octahedral Re(6)C(CO)(18) core capped by a Ru(CO)(3) fragment. The visible spectrum of [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] shows a broad, strong band at 670 nm (epsilon = 8100), whereas all of the absorptions of [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)] are at higher energy. An irreversible oxidation wave with E(p) at 0.34 V is observed for [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)], whereas two quasi-reversible oxidation waves with E(1/2) values of 0.21 and 0.61 V (vs Ag/AgCl) are observed for [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)]. The molybdenum cap in [Re(6)C(CO)(18)Mo(CO(4))](2-) is cleaved by heating in donor solvents, and by treatment with H(2), to give largely [H(2)Re(6)C(CO)(18)](2-). In contrast, [Re(6)C(CO)(18)Ru(CO)(3)](2-) shows no tendency to react under similar conditions.

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Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Comparative Properties of [PPN]₂[Re₆C(CO)₁₈Mo(CO)₄] and [PPN]₂[Re₆C(CO)₁₈Ru(CO)₃]

1996

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Bimetallic Effects on the Redox Activity of Transition‐Metal Carbonyl Clusters

Zanello¹,

Biani²

1999

Metal Clusters in Chemistry

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Substitution and Insertion Reactions

Twigg

1994

Mechanisms of Inorganic and Organometallic Reactions

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Oxidatively enhanced intramolecular carbonyl scrambling in the mixed-metal cluster [Re7C(CO)21Rh(CO)2]2-

Cited by 7 publications

References 1 publication

Synthesis, Characterization, and Comparative Properties of [PPN]₂[Re₆C(CO)₁₈Mo(CO)₄] and [PPN]₂[Re₆C(CO)₁₈Ru(CO)₃]

Synthesis, Characterization, and Comparative Properties of [PPN]₂[Re₆C(CO)₁₈Mo(CO)₄] and [PPN]₂[Re₆C(CO)₁₈Ru(CO)₃]

Bimetallic Effects on the Redox Activity of Transition‐Metal Carbonyl Clusters

Substitution and Insertion Reactions

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Oxidatively enhanced intramolecular carbonyl scrambling in the mixed-metal cluster [Re7C(CO)21Rh(CO)2]2-

Cited by 7 publications

References 1 publication

Synthesis, Characterization, and Comparative Properties of [PPN]2[Re6C(CO)18Mo(CO)4] and [PPN]2[Re6C(CO)18Ru(CO)3]

Synthesis, Characterization, and Comparative Properties of [PPN]2[Re6C(CO)18Mo(CO)4] and [PPN]2[Re6C(CO)18Ru(CO)3]

Bimetallic Effects on the Redox Activity of Transition‐Metal Carbonyl Clusters

Substitution and Insertion Reactions

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Product

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Synthesis, Characterization, and Comparative Properties of [PPN]₂[Re₆C(CO)₁₈Mo(CO)₄] and [PPN]₂[Re₆C(CO)₁₈Ru(CO)₃]

Synthesis, Characterization, and Comparative Properties of [PPN]₂[Re₆C(CO)₁₈Mo(CO)₄] and [PPN]₂[Re₆C(CO)₁₈Ru(CO)₃]