Synthesis and reactivity of a heterometallic carbon dioxide complex

Lundquist, Eric G.; Huffman, John C.; Folting, Kirsten; Mann, Brian E.; Caulton, Kenneth G.

doi:10.1021/ic00326a026

Cited by 34 publications

(7 citation statements)

References 5 publications

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“…Caulton et al reported and structurally characterized the cluster compound 100 by the direct reaction of CO 2 with two equivalents of (COD)RhH 3 Os(PMe 2 Ph) 3 . The reaction also yields H 3 Os(CO)(PMe 2 Ph) 3 and water as reaction products.…”

Section: μ3-η3 Complexesmentioning

confidence: 99%

“…Only one compound of this type has been reported. Caulton et al 57b showed that the μ 3 -η 3 complex 100 would react with ZnBr 2 to afford a compound in which both carboxyl oxygens were bound to zinc; the compound ( 102 ) was structurally characterized (see section IV.H).…”

Section: μ4-η5 Complexesmentioning

confidence: 99%

“…Caulton et al reported the characterization of [(COD)Rh] 2 OsH 2 (CO 2 )(PMe 2 Ph) 3 ( 100 ), which has the carboxylate carbon bound to the osmium center. The bonding of the CO 2 ligand is highly symmetrical, with C−O bond lengths slightly greater (1.300(21) and 1.309(22) Å) than in the previous examples and with essentially equal O−Rh bond lengths (2.062(13) and 2.065(12) Å).…”

Section: E μ3-η3 Complexesmentioning

confidence: 99%

“…Caulton et al reported the trinuclear compound [(COD)Rh] 2 (CO 2 )OsH 2 (PMe 3 Ph) 3 ( 100 ), which exhibited μ 3 -η 3 bonding of the bridging CO 2 ligand. The compound showed ν OCO bands at 1365 and 1260 cm -1 which were identified with the help of isotopic labeling studies.…”

Section: μ3-η3 Complexesmentioning

confidence: 99%

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The Organometallic Chemistry of Carbon Dioxide

1996

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Section: μ3-η3 Complexesmentioning

confidence: 99%

Section: μ4-η5 Complexesmentioning

confidence: 99%

Section: E μ3-η3 Complexesmentioning

confidence: 99%

Section: μ3-η3 Complexesmentioning

confidence: 99%

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The Organometallic Chemistry of Carbon Dioxide

1996

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“…Zn occurs in kidney bean phosphatase in combination with iron [14] and in combination with copper in proteins obtained from rat liver [15]. The efficacy of heterobimetallic complexes in asymmetric activation of carbon dioxide and related molecules has been demonstrated [16]. Further, heterobimetallic complexes have potential to mediate chemical reactions of industrial relevance either more efficiently than or, in a different manner to, isolated metal centers [17].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of heterobimetallic Ni(II)–Zn(II) complexes from bis(2-hydroxy-1 -naphthaldehyde)succinoyldihydrazone

Lal¹,

Chakraborty²,

Chanu³

et al. 2010

Journal of Coordination Chemistry

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Monometallic zinc(II) and nickel(II) complexes, [Zn(H 2 nsh)(H 2 O)] (1) and [Ni(H 2 nsh)(H 2 O) 2 ](2), have been synthesized in methanol by template method from bis(2-hydroxy-1-naphthaldehyde)succinoyldihydrazone (H 4 nsh). Reaction of monometallic complexes with alternate metal(II) acetates as a transmetallator in 1 : 3 molar ratio resulted in the formation of heterobimetallic complexes [NiZn(nsh)(A) 3 ] and [ZnNi(nsh)(A 0 ) 2 ] (A ¼ H 2 O (3), py (4), 2-pic (5), 3-pic (6), 4-pic (7)), (A 0 ¼ H 2 O (8), py (9), 2-pic (10), 3-pic (11), and 4-pic (12)). The complexes have been characterized by elemental analyzes, mass spectra, molar conductance, magnetic moments, electronic, EPR, and IR spectroscopies. All of the complexes are non-electrolytes. Monometallic zinc(II) is diamagnetic while monometallic nickel(II) complex and all heterobimetallic complexes are paramagnetic. The metal centers in heterobimetallic complexes are tethered by dihydrazone and naphthoxo bridging. Zinc(II) is square pyramidal; nickel(II) is six-coordinate distorted octahedral except [ZnNi(nsh)(A) 2 ], in which nickel(II) has square-pyramidal geometry. The displacement of metal center in monometallic complexes by metal ion has been observed in the resulting heterobimetallic complexes.

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Mapping the Transformation [{Ru^II(CO)₃Cl₂}₂]→[Ru^I₂(CO)₄]²⁺: Implications in Binuclear Water–Gas Shift Chemistry

Majumdar

Sinha

Ghatak

et al. 2010

Chemistry A European J

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The complete sequence of reactions in the base-promoted reduction of [{Ru(II)(CO)(3)Cl(2)}(2)] to [Ru(I) (2)(CO)(4)](2+) has been unraveled. Several mu-OH, mu:kappa(2)-CO(2)H-bridged diruthenium(II) complexes have been synthesized; they are the direct results of the nucleophilic activation of metal-coordinated carbonyls by hydroxides. The isolated compounds are [Ru(2)(CO)(4)(mu:kappa(2)-C,O-CO(2)H)(2)(mu-OH)(NP(F)-Am)(2)][PF(6)] (1; NP(F)-Am=2-amino-5,7-trifluoromethyl-1,8-naphthyridine) and [Ru(2)(CO)(4)(mu:kappa(2)-C,O-CO(2)H)(mu-OH)(NP-Me(2))(2)][BF(4)](2) (2), secured by the applications of naphthyridine derivatives. In the absence of any capping ligand, a tetranuclear complex [Ru(4)(CO)(8)(H(2)O)(2)(mu(3)-OH)(2)(mu:kappa(2)-C,O-CO(2)H)(4)][CF(3)SO(3)](2) (3) is isolated. The bridging hydroxido ligand in 1 is readily replaced by a pi-donor chlorido ligand, which results in [Ru(2)(CO)(4)(mu:kappa(2)-C,O-CO(2)H)(2)(mu-Cl)(NP-PhOMe)(2)][BF(4)] (4). The production of [Ru(2)(CO)(4)](2+) has been attributed to the thermally induced decarboxylation of a bis(hydroxycarbonyl)-diruthenium(II) complex to a dihydrido-diruthenium(II) species, followed by dinuclear reductive elimination of molecular hydrogen with the concomitant formation of the Ru(I)--Ru(I) single bond. This work was originally instituted to find a reliable synthetic protocol for the [Ru(2)(CO)(4)(CH(3)CN)(6)](2+) precursor. It is herein prescribed that at least four equivalents of base, complete removal of chlorido ligands by Tl(I) salts, and heating at reflux in acetonitrile for a period of four hours are the conditions for the optimal conversion. Premature quenching of the reaction resulted in the isolation of a trinuclear Ru(I) (2)Ru(II) complex [{Ru(NP-Am)(2)(CO)}{Ru(2)(NP-Am)(2)(CO)(2)(mu-CO)(2)}(mu(3):kappa(3)-C,O,O'-CO(2))][BF(4)](2) (6). These unprecedented diruthenium compounds are the dinuclear congeners of the water-gas shift (WGS) intermediates. The possibility of a dinuclear pathway eliminates the inherent contradiction of pH demands in the WGS catalytic cycle in an alkaline medium. A cooperative binuclear elimination could be a viable route for hydrogen production in WGS chemistry.

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Synthesis and reactivity of a heterometallic carbon dioxide complex

Cited by 34 publications

References 5 publications

The Organometallic Chemistry of Carbon Dioxide

The Organometallic Chemistry of Carbon Dioxide

Synthesis and characterization of heterobimetallic Ni(II)–Zn(II) complexes from bis(2-hydroxy-1 -naphthaldehyde)succinoyldihydrazone

Mapping the Transformation [{Ru^II(CO)₃Cl₂}₂]→[Ru^I₂(CO)₄]²⁺: Implications in Binuclear Water–Gas Shift Chemistry

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Synthesis and reactivity of a heterometallic carbon dioxide complex

Cited by 34 publications

References 5 publications

The Organometallic Chemistry of Carbon Dioxide

The Organometallic Chemistry of Carbon Dioxide

Synthesis and characterization of heterobimetallic Ni(II)–Zn(II) complexes from bis(2-hydroxy-1 -naphthaldehyde)succinoyldihydrazone

Mapping the Transformation [{RuII(CO)3Cl2}2]→[RuI2(CO)4]2+: Implications in Binuclear Water–Gas Shift Chemistry

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Mapping the Transformation [{Ru^II(CO)₃Cl₂}₂]→[Ru^I₂(CO)₄]²⁺: Implications in Binuclear Water–Gas Shift Chemistry