Carbon dioxide insertion into the iron-zirconium and ruthenium-zirconium bonds of the heterobimetallic complexes Cp(CO)2MZr(Cl)Cp2: direct production of the .mu.-.eta.1(C):.eta.2(O,O')-CO2 compounds Cp(CO)2MCO2Zr(Cl)Cp2

Pinkes, John R.; Steffey, Bryan D.; Vites, Jose C.; Cutler, Alan R.

doi:10.1021/om00013a009

Cited by 73 publications

(52 citation statements)

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“…The NCS heteroallene, linear in the free isothiocyanate, is bent in 12 [N(4)-C(2)-S(1) 112(1)8] and bridges the metals in a manner similar to that found in the CS 2 analogue 9 a. Whereas the CÀS bond length of 1.745 (17) lies in the range of a CÀS single bond, the carbon ± nitrogen bond [1.307 (22) ] retains considerable double bond character. [19] Reactions of the heterodinuclear complexes with esters and aldehydes: The reactions described in the previous section lead to stable products of insertions into the polar metal ± metal bond.…”

Section: Resultsmentioning

confidence: 95%

“…The first such reaction was reported in a study by Culter and coworkers, [17] who showed that Caseys ZrÀM heterobimetallic complexes insert CO 2 into their metal ± metal bond, while Bergman et al studied the reactions of an imido-bridged IrÀZr complex with CO 2 , CS 2 and MeNCS, the last two undergoing fragmentation in the course of the reaction. [18] We have previously reported the insertion of isonitriles into the polar metal ± metal bond of early ± late heterobimetallic complexes that are related to those reported in this paper.…”

Section: Resultsmentioning

confidence: 99%

“…[30] Attempts to study the kinetics of this reaction and thus gain additional insight concerning its mechanism were precluded by the extreme rapidity of the conversion and the air and moisture sensitivity of the compounds involved. However, given the results of the 13 C and 17 O labeling studies, we propose the reaction mechanism for this transformation displayed in Scheme 11. Scheme 11.…”

Section: Reactions Of the Heterodinuclear Complexes With Ketonesmentioning

confidence: 92%

“…17 O nucleus in a metallacarboxy environment. [30] Attempts to study the kinetics of this reaction and thus gain additional insight concerning its mechanism were precluded by the extreme rapidity of the conversion and the air and moisture sensitivity of the compounds involved.…”

Section: Reactions Of the Heterodinuclear Complexes With Ketonesmentioning

confidence: 99%

“…An closely related example of such a species was recently characterized by X-ray crystallography the structure of which could therefore be unambiguously established. [28] As in the reaction of 5 with 1,2-diphenylcyclopropenone discussed above, the oxygen transfer from the sulfoxide to the carbonyl ligand, which is converted to the m-CO 2 unit, was proved by using 13 17 O nucleus in a metallacarboxylato environment. [30] …”

Section: Reactions Of the Heterodinuclear Complexes With Ketonesmentioning

confidence: 99%

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Cooperative Reactivity of Early-Late Heterodinuclear Transition Metal Complexes with Polar Organic Substrates

et al. 2000

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A comprehensive investigation into the cooperative reactivity of two chemically complementary metal-complex fragments in early-late heterodinuclear complexes has been carried out. Reaction of the partially fluorinated tripodal amidozirconium complexes [HC-(SiMe2NR)3Zr(mu-Cl)2Li(OEt2)2] (R = 2-FC6H4: 2a, 2,3,4-F3C6H4: 2b) with K[CpM(CO)2] (M=Fe, Ru) afforded the stable metal-metal bonded heterodinuclear complexes [HC[SiMe2NR]3-Zr-MCp(CO)2] (3-6). Reaction of the dinuclear complexes with methyl isonitrile as well as the heteroallenes CO2, CS2, RNCO and RNCS led to insertion into the polar metal-metal bond. Two of these complexes, [HC[SiMe2N(2-FC6-H4)]3Zr(S2C)Fe(CO)2Cp] (9a) and [HC-[SiMe2N(2-FC2H4)]3Zr-(SCNPh)Fe(CO)2-Cp] (12), have been structurally characterized by a single crystal X-ray structure analysis, proving the structural situation of the inserted substrate as a bridging ligand between the early and late transition metal centre. The reactivity towards organic carbonyl derivatives proved to be varied. Reaction of the heterobimetallic complexes with benzyl and ethylbenzoate led to the cleavage of the ester generating the respective alkoxozirconium complexes [HC[SiMe2N(2-FC6H4)]3ZrOR] (R = Ph-CH2: 13a, Et: 13b) along with [CpFe-[C(O)Ph](CO)2], whereas the analogous reaction with ethyl formate gave 13b along with [CpFeH(CO)2]; this latter complex results from the instability of the formyliron species initially formed. Aryl aldehydes were found to react with the Zr-M complexes according to a Cannizzaro disproportionation pattern yielding the aroyliron and ruthenium complexes along with the respective benzoxyzirconium species. The transfer of the aldehyde hydrogen atom in the course of the reaction was established in a deuteriation experiment. [HC[SiMe2-N(2-FC6H4)]3Zr-M(CO)2Cp] reacted with lactones to give the ring-opened species containing an alkoxozirconium and an acyliron or acylruthenium fragment; the latter binds to the early transition metal centre through the acyl oxygen atom, as evidenced from the unusuallly low-field shifted 13C NMR resonances of the RC(O)M units. Ketones containing a-CH units react with the Zr-Fe complexes cooperatively to yield the aldol coupling products coordinated to the zirconium complex fragment along with the hydridoiron compound [CpFeH(CO)2], whereas 1,2-diphenylcyclopropenone underwent an oxygen transfer from the keto group to a CO ligand to give a linking CO2 unit and a cyclopropenylidene ligand coordinated to the iron fragment in [HC-[Si(CH3)2N(2,3,4-F3C6H2)]3Zr(mu-O2C)-Fe(CO)[C3Ph2)Cp] (19). The atom transfer was established by 17O and 13C labelling studies. Similar oxygen-transfer processes were observed in the reactions with pyridine N-oxide, dimethylsulfoxide and methylphenylsulfoxide.

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Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 99%

Section: Reactions Of the Heterodinuclear Complexes With Ketonesmentioning

confidence: 92%

Section: Reactions Of the Heterodinuclear Complexes With Ketonesmentioning

confidence: 99%

Section: Reactions Of the Heterodinuclear Complexes With Ketonesmentioning

confidence: 99%

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Cooperative Reactivity of Early-Late Heterodinuclear Transition Metal Complexes with Polar Organic Substrates

et al. 2000

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Stark polare Metall-Metall-Bindungen in Heterodimetallkomplexen des „Early-Late”-Typs

Gade

2000

Angewandte Chemie

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Bindungspolarität in ihrer extremsten Form in Metall‐Metall‐Bindungen der Übergangsmetalle findet man in Zwei‐ und Mehrkernkomplexen, in denen Komplexfragmente der Metalle von beiden Enden des d‐Blocks im Periodensystem direkt aneinander gebunden sind. Diese Verknüpfung von Metallzentren mit sehr unterschiedlichen redoxchemischen Eigenschaften durch eine direkte Metall‐Metall‐Bindung war lange Zeit eine große Herausforderung für den präparativ arbeitenden Komplexchemiker. Die Unterdrückung von Reaktionswegen, die über Einelektronentransfer zur Zersetzung der Komplexe führen, sowie die Abschirmung der hochgradig Lewis‐aciden frühen Übergangsmetalle durch geeignet konzipierte Ligandensphären haben die systematische Erforschung dieser Verbindungsklasse erst ermöglicht. Zeitgleich mit dieser Entwicklung haben jüngste konzeptionelle Fortschritte bei der theoretischen Beschreibung der Bindungspolarität unser Verständnis der Eigenschaften dieser Metall‐Metall‐Bindungen verfeinert. Den stärksten Anreiz für die Entwicklung auf diesem Gebiet bietet die Untersuchung der kooperativen Reaktivität zweier oder mehrerer Koordinationszentren gegenüber organischen Substraten. Diese Kooperativität, die sich in den unterschiedlichen Funktionen der Metalle bei der Umwandlung organischer Verbindungen manifestierte, bietet vielversprechende Ansätze für die Entwicklung neuer stöchiometrischer oder sogar katalytischer Reaktionstypen.

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Highly Polar Metal-Metal Bonds in “Early-Late” Heterodimetallic Complexes

Gade

2000

Angew. Chem. Int. Ed.

255

147

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Carbon dioxide insertion into the iron-zirconium and ruthenium-zirconium bonds of the heterobimetallic complexes Cp(CO)2MZr(Cl)Cp2: direct production of the .mu.-.eta.1(C):.eta.2(O,O')-CO2 compounds Cp(CO)2MCO2Zr(Cl)Cp2

Cited by 73 publications

References 0 publications

Cooperative Reactivity of Early-Late Heterodinuclear Transition Metal Complexes with Polar Organic Substrates

Cooperative Reactivity of Early-Late Heterodinuclear Transition Metal Complexes with Polar Organic Substrates

Stark polare Metall-Metall-Bindungen in Heterodimetallkomplexen des „Early-Late”-Typs

Highly Polar Metal-Metal Bonds in “Early-Late” Heterodimetallic Complexes

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