Novel carbene complexes from triphenyl- and trimethyl-germylpentacarbonylmanganese

Webb, M. J.; Stewart, Robert P.; Graham, W. A. G.

doi:10.1016/s0022-328x(00)95007-1

Cited by 29 publications

(6 citation statements)

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“…The reaction of 2 in CH 2 Cl 2 with electrophilic methylating reagents, [Me 3 O + ][BF 4 - ], MeSO 3 CF 3 , MeI, or [(MeO) 2 CH + ][PF 6 - ] (from 1:1 [Ph 3 C + ][PF 6 - ]/(MeO) 3 CH), produces acyl 3 in part, which is expected in view of the conversion of 2 to 3 , but no [(η 5 -C 5 H 4 CH 2 CH 2 Me)Fe(CO) 3 + ] [X - ] ( 6 ·X, X = BF 4 , SO 3 CF 3 , I, or PF 6 ) is formed. With [Me 3 O + ][BF 4 - ], [(η 5 -C 5 H 4 CH 2 CH 3 )Fe(CO) 3 + ][BF 4 - ] ( 7 ·BF 4 ) is formed, and with [Ph 3 C + ][PF 6 - ]/(MeO) 3 CH, 5 ·PF 6 is the product.…”

Section: Resultsmentioning

confidence: 99%

Ring Opening of (Spiro[2.4]hepta-4,6-diene)tricarbonyliron: A Revisit

Chao

Liu

1998

Organometallics

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Spiro[2.4]hepta-4,6-diene)tricarbonyliron (2) self-converts to the tethered acyl complex (CO) 2 FeC(O)CH 2 CH 2 (η 5 -C 5 H 4 ) (3) when refluxed for 1 h in common organic solvents. The reaction of 2 with an external electrophile (CPh 3 + , H + ) opens the three-membered ring, resulting in the cation (η 5 -C 5 H 4 CH 2 CH 2 R)Fe(CO) 3 + whose structure was determined by spectroscopic methods and confirmed by X-ray analysis of the PPh 3 derivative (η 5 -C 5 H 4 CH 2 -CH 3 )Fe(CO) 2 (PPh 3 ) + . The reaction of 3 with a strong electrophile (CPh 3 + , Me + ) affords the rotationally restricted Fe-(alkoxy)carbene cation (CO) 2 FedC(OR)CH 2 CH 2 (η 5 -C 5 H 4 ) + , which can be converted to the Fe-(anilino)carbene cation (CO) 2 FedC(NHPh)CH 2 CH 2 (η 5 -C 5 H 4 ) + . 146 °C) originating from 4. If brought to reflux for 1 h, compound 2 in solution is fully converted to 3, whose IR ν(CO) stretching bands are shown in Figure 1d. Compound 3 is not soluble in n-hexane or Et 2 O but is soluble in THF and chlorinated solvents.Reactions of 2 with Lewis and Protic Acids. Scheme 1 shows a proposed, intramolecular, ionic rear-

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Section: Resultsmentioning

confidence: 99%

Ring Opening of (Spiro[2.4]hepta-4,6-diene)tricarbonyliron: A Revisit

Chao

Liu

1998

Organometallics

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“…The information given for each compound is as follows: elements for which satisfactory analyses were obtained, yield (%), color (Y = yellow, O = orange, G = light green), melting point (°C, uncorrected). Correct parent ion peaks were observed in the mass spectrum for all nonionic compounds 6. Ionic compounds in tetrahydrofuran; nonionic compounds in «-heptane, except 20 in chloroform.…”

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confidence: 88%

“…The only such compounds which have been reported previously are (C6-H5)3SnCo(CO)3C(OC2H5)C6H5,5 (C6H5)3PbCo(CO)3C(0-C2H5)C6H5,5 and (C6H5)3GeMn(CO)4C(OC2H5)CH3. 6 An account has been published previously of the reaction of the [(C6H5)3GeMn(CO)4COCH3]" ion with H+ to give cyclic germyloxycarbenes6, and we were curious to determine whether such behavior would be observed for complexes of other metals.…”

Section: Introductionmentioning

confidence: 99%

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Carbene derivatives of molybdenum and tungsten containing metal-metal bonds

Dean¹,

Graham²

1977

Inorg. Chem.

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“…A number of compounds with an unusual cyclic structure of the type 1 have been prepared (1,2), and in some cases have been shown by nmr spectroscopy to exist as equilibrium mixtures of dimeric and monomeric forms in solution (3, 4). A series of complexes with noncyclic structures of the type 2 has also been R?…”

Section: Introductionmentioning

confidence: 99%

The reactivity of cyclic germoxycarbene complexes of manganese and rhenium towards nucleophiles

Webb¹,

Graham²

1976

Can. J. Chem.

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. Can. J. Chem. 54, 2557Chem. 54, (1976. Several acylate salts and noncyclic carbene complexes of manganese and rhenium, containing organogermanium ligands, have been prepared via the reactions of the cyclic germoxycarbene complexes of empirical formula Ph2GeM(C0)4COMe (M = Mn, Re) with the nucleophiles methyllithium or methoxide ion. In each case the observed product could be rationalized in terms of nucleophilic attack at germanium. Treatment of Ph2GeRe(C0)4COMe with methyllithium, followed by ethylation with aqueous Et30BF4, afforded ~is-Ph~MeGeRe(C0)~C-(0Et)Me. The manganese analog of this product could be obtained if excess methyllithium were used in the first step. The use of a deficit of methyllithium, however, followed by ethylation, yielded ci~-Ph~FGeMn(C0)~C(0Et)Me. Solution infrared spectra have indicated that lithium methoxide and lithium bromide impurities in the methyllithium are involved in this reaction. The reaction of Ph2GeMn(C0)4COMe with sodium methoxide is presumed to involve nucleophilic attack at germanium to give a methoxygermanium species. Subsequent treatment with aqueous tetraethylammonium bromide gave the hydroxygermanium complex, [cis-Ph2(HO)-GeMn(C0)4C (0) 54, 2557 (1976). On a prkpark plusieurs sels acylates et plusieurs complexes de carbene non cyclique du manganbe et du rhknium contenant des ligands organogermanium en faisant intervenir les rB actions de complexes de germoxycarbkne cyclique de structure brute Ph2GeM(CO)4COMe (M = Mn, Re) avec les nuclkophiles methyllithium ou ion methylate. Dans chaque cas, le produit observk peut &tre rationalisk en terme d'une attaque nuclkophile au site du germanium. La rhction du Ph2GeRe(C0)4COMe avec le mCthyllithium suivi par une rhction d'kthylation avec le Et30BF4 aqueux conduit au Ph2MeGeRe(C0)4C(OEt)Me cis. On peut aussi obtenir I'analogue avec du manganbe de ce composk si l'on utilise un excb de mkthyllithium dans la premikre ktape. L'utilisation d'une quantitk dkficiente de mkthyllithium suivie par une kthylation conduit toutefois au Ph2FGeMn(C0)4C(OEt)Me cis. Des spectres infrarouges en solution indiquent que des impuretk de mkthylate de lithium et de bromure de lithium dans le mkthyllithium sont impliquks dans cette rhction. On fait I'hypothbe que la rhction du Ph2GeMn-(C0)4COMe avec le mkthylate de sodium implique une attaque nuclkophile au niveau du germanium pour conduire ? I des espkces mkthoxygermanium. Un traitement ultkrieur avec du bromure de tktrakthylammonium aqueux conduit au complexe hydroxygermanium [Phl(OH)-GeMn(CO)4C (0) IntroductionIn recent papers we have described the synthesis and characterisation of a number of carbene complexes of manganese and rhenium which also contain organogermanium or organotin ligands. A number of compounds with an unusual cyclic structure of the type 1 have been

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Novel carbene complexes from triphenyl- and trimethyl-germylpentacarbonylmanganese

Cited by 29 publications

References 5 publications

Ring Opening of (Spiro[2.4]hepta-4,6-diene)tricarbonyliron: A Revisit

Ring Opening of (Spiro[2.4]hepta-4,6-diene)tricarbonyliron: A Revisit

Carbene derivatives of molybdenum and tungsten containing metal-metal bonds

The reactivity of cyclic germoxycarbene complexes of manganese and rhenium towards nucleophiles

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