Structures of two compounds containing strong metal-to-metal bonds

Bennett, Michael J.; Cotton, F. Albert; Foxman, Bruce M.; Stokely, Peter F.

doi:10.1021/ja00987a059

Cited by 44 publications

(9 citation statements)

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“…Most of the distances and angles in the molecule of 3 (Table ) are in fair agreement with those in other known structures in the 1,7-Re 2 Cl 6 (PR 3 ) 2 class. ,, Again, however, we have found some very large discrepancies between the disordered and ordered structures. We expected to see a trans effect such that the Re−Cl bonds trans to Re−P bonds would be longer than cis ones.…”

Section: Resultssupporting

confidence: 85%

Mixed Chloride Phosphine Complexes of Dirhenium Cores. 1. New Reactions and Unprecedented Structures Involving Trimethylphosphine

1997

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The unusual 1,2,7-isomer of Re2Cl5(PMe3)3 (1) has been used as a starting material to prepare previously unknown dirhenium complexes. One-electron reduction of 1 by cobaltocene followed by nonredox substitution of the resulting anionic species with PMe3 led to the formation of a triply bonded 1,2,7,8-Re2Cl4(PMe3)4 (2). In the crystal structure of 2, phosphine ligands on both metal centers exhibit a cis arrangement with a P−Re−P angle of 93.3° in contrast to the well-known type of 1,3,6,8-isomers with a trans arrangement of the monodentate phosphines connected to each metal atom. Complex 2 represents the first example of an isomer of this type in the large M2X4(PR3)4 class of compounds (M = Re, Tc, W, Mo; X = Cl, Br, I; PR3 = monodentate phosphine). The one-electron oxidation product of 1 cocrystallized with one molecule of tetrabutylammonium chloride afforded Re2Cl6(PMe3)2 (3), for which all previous synthetic attempts had failed. This quadruply bonded complex exhibits an unusual 3-fold disorder of the Re2 unit with equal populations for all three orientations. We also report that when the “classic” reaction of octachlorodirhenate anion, Re2Cl8 2-, with trimethylphosphine is carried out in benzene at room temperature the reduction processes do not occur and the product is a novel paramagnetic complex, Re2Cl6(PMe3)4 (4), which does not have a metal−metal bond (the Re−Re separation is 3.8476(4) Å). Another interesting feature of compound 4 is that the PMe3 ligands have a cis disposition at each rhenium center and are located in the same plane as the metal atoms and bridging chlorine ligands. For such a ligand arrangement the molecule of 4 is the only example of a nonmetal−metal-bonded dinuclear compound with monodentate phosphine ligands.

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Section: Resultssupporting

confidence: 85%

Mixed Chloride Phosphine Complexes of Dirhenium Cores. 1. New Reactions and Unprecedented Structures Involving Trimethylphosphine

1997

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“…CoP + 02 CoP O, (7) This reaction is not favorable enough to study quantitatively at any accessible temperature in which the solvent is liquid (down to -95°in toluene), and thus it is quite unfavorable in comparison to reactions 3 and 4. A solution of Co(p-OCH3)TPP in toluene containing 1 atm of air at -83.5°showed a detectable amount of its "base-off" 02 adduct. This suggests that the equilibrium constant for reaction 7 is at least 100 times smaller than the "base on" 02 adduct at that temperature.…”

Section: Discussionmentioning

confidence: 99%

Reactions of monomeric cobalt-oxygen complexes. I. Thermodynamics of reaction of molecular oxygen with five- and six-coordinate amine complexes of a cobalt porphyrin

Walker¹

1973

J. Am. Chem. Soc.

132

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“…-5 (8) 1 (5) 1C(1) 16 (12) 16 ( 6) 48 ( 12) 1( 7) -17 (15) 44 ( 15) 1 (9) 1C( 5) 94 ( 26) 35 (10) 78 ( 19)…”

Section: Methodsunclassified

“…-10( 5) 3C( 3) 65 ( 18) 18 ( 6) 20 ( 8) 11 ( 9) 1 (10) 2( 6) 3C( 4) 44 ( 16) 19 (6) 30 (10) -5 (8) -2(10) 1 (7) 3C( 5) 104 ( 29) 64 ( 15) 37 ( 13) 25 ( 17) 42 ( 16) 24 ( 12) 3C( 6) 32 ( 14) 25 ( 7) 32 (10) 4…”

Section: Methodsunclassified

Preparation and structure of a multiply bonded dirhenium(5+) species bridged by two diphosphinomethane ligands

Cotton¹,

Shive²,

Stults³

1976

Inorg. Chem.

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Structures of two compounds containing strong metal-to-metal bonds

Cited by 44 publications

References 0 publications

Mixed Chloride Phosphine Complexes of Dirhenium Cores. 1. New Reactions and Unprecedented Structures Involving Trimethylphosphine

Mixed Chloride Phosphine Complexes of Dirhenium Cores. 1. New Reactions and Unprecedented Structures Involving Trimethylphosphine

Reactions of monomeric cobalt-oxygen complexes. I. Thermodynamics of reaction of molecular oxygen with five- and six-coordinate amine complexes of a cobalt porphyrin

Preparation and structure of a multiply bonded dirhenium(5+) species bridged by two diphosphinomethane ligands

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