The parent compounds trans-[Mo(salophen)Cl-2] 1 [salophen = N,N'-bis(salicylidene)-o-phenylenediamine dianion] and trans-[Mo(tbsalophen)Cl-2] 2 [tbsalophen = N,N'-bis(3,5-di-tert-butylsalicylidene)-o-phenylenediamine dianion] were obtained from the corresponding Schiff bases and [MoCl4(MeCN)(2)]. The alkylation of 1 proceeded very differently depending on the alkylating agent. The reaction with (PhCH2)(2)Mg led to the formation of trans-[Mo(salophen)(PhCH2)(2)] 3, containing two alkyl groups at the metal, while with Mg(mes)Br (mes = 2,4,6-Me3C6H2) arylation occurred both at the imino carbons and at the metal, via a rather complex mechanism. Reduction of 1 led to an intermediate Mo(salophen), which was intercepted by PhCCPh. The plausible intermediate metallocyclopropene rearranged with the migration of one of the carbons to an imino group and dimerization of the monomeric unit. The salophen ligand displayed a bridging bonding mode in the dimer, containing a Mo=Mo fragment and two bridging vinyl functionalities. The proposed structures are supported by three X-ray analyses.

Molybdenum–carbon functionalities supported by a quadridentate Schiff-base ligand: the reactivity of trans-dichloro[N,N′-bis(salicylidene)-o-phenylenediaminato]molybdenum(IV) / Solari, E; Maltese, C; Latronico, M; Floriani, C; Chiesi-Villa, A; Rizzoli, C. - In: JOURNAL OF THE CHEMICAL SOCIETY DALTON TRANSACTIONS. - ISSN 0300-9246. - STAMPA. - 14:(1998), pp. 2395-2400. [10.1039/a802148a]

Molybdenum–carbon functionalities supported by a quadridentate Schiff-base ligand: the reactivity of trans-dichloro[N,N′-bis(salicylidene)-o-phenylenediaminato]molybdenum(IV)

Latronico M;
1998-01-01

Abstract

The parent compounds trans-[Mo(salophen)Cl-2] 1 [salophen = N,N'-bis(salicylidene)-o-phenylenediamine dianion] and trans-[Mo(tbsalophen)Cl-2] 2 [tbsalophen = N,N'-bis(3,5-di-tert-butylsalicylidene)-o-phenylenediamine dianion] were obtained from the corresponding Schiff bases and [MoCl4(MeCN)(2)]. The alkylation of 1 proceeded very differently depending on the alkylating agent. The reaction with (PhCH2)(2)Mg led to the formation of trans-[Mo(salophen)(PhCH2)(2)] 3, containing two alkyl groups at the metal, while with Mg(mes)Br (mes = 2,4,6-Me3C6H2) arylation occurred both at the imino carbons and at the metal, via a rather complex mechanism. Reduction of 1 led to an intermediate Mo(salophen), which was intercepted by PhCCPh. The plausible intermediate metallocyclopropene rearranged with the migration of one of the carbons to an imino group and dimerization of the monomeric unit. The salophen ligand displayed a bridging bonding mode in the dimer, containing a Mo=Mo fragment and two bridging vinyl functionalities. The proposed structures are supported by three X-ray analyses.
1998
Molybdenum–carbon functionalities supported by a quadridentate Schiff-base ligand: the reactivity of trans-dichloro[N,N′-bis(salicylidene)-o-phenylenediaminato]molybdenum(IV) / Solari, E; Maltese, C; Latronico, M; Floriani, C; Chiesi-Villa, A; Rizzoli, C. - In: JOURNAL OF THE CHEMICAL SOCIETY DALTON TRANSACTIONS. - ISSN 0300-9246. - STAMPA. - 14:(1998), pp. 2395-2400. [10.1039/a802148a]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11589/8285
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