Title

Reactions of Rhenium and Manganese Carbonyl Complexes with 1,8-bis(diphenylphosphino)naphthalene: Ligand Chelation, C–H and C–P bond-cleavage Reactions

Document Type

Article

Language

eng

Publication Date

8-1-2008

Publisher

Elsevier

Source Publication

Journal of Organometallic Chemistry

Source ISSN

0022-328X

Abstract

Reaction of [Re2(CO)8(MeCN)2] with 1,8-bis(diphenylphosphino)naphthalene (dppn) afforded three mono-rhenium complexes fac-[Re(CO)311-PPh2C10H6)(PPh2H)] (1), fac-[Re(CO)3111-(O)PPh2C10H6(O)PPh(C6H4)}] (2) and fac-[ReCl(CO)32-PPh2C10H6PPh2)] (3). Compounds 13 are formed by Re–Re bond cleavage and P–C and C–H bond activation of the dppn ligand. Each of these three complexes have three CO groups arranged in facial fashion. Compound 1 contains a chelating cyclometalated diphenylnaphthylphosphine ligand and a terminally coordinated PPh2H ligand. Compound 2 consists of an orthometalated dppn-dioxide ligand coordinated in a κ111-fashion via both the oxygen atoms and ortho-carbon atom of one of the phenyl rings. Compound 3 consists of an unchanged chelating dppn ligand and a terminal Cl ligand. Treatment of [Mn2(CO)8(MeCN)2] with a slight excess of dppn in refluxing toluene at 72 °C, gave the previously reported [Mn2(CO)8(μ-PPh2)2] (4), formed by cleavage of C–P bonds, and the new compound fac-[MnCl(CO)32-PPh2C10H6PPh2)] (5), which has an unaltered chelating dppn and a terminal Cl ligand. In sharp contrast, reaction of [Mn2(CO)8(MeCN)2] with slight excess of dppn at room temperature yielded the dimanganese [Mn2(CO)91-PPh2(C10H7)}] (6) in which the diphenylnaphthylphosphine ligand, formed by facile cleavage of one of the P–C bonds, is axially coordinated to one Mn atom. Compound 6 was also obtained from the reaction of [Mn2(CO)9(MeCN)] with dppn at room temperature. The XRD structures of complexes 13, 5, 6 are reported.

Comments

Journal of Organometallic Chemistry, Vol. 693, No. 16 (August 1, 2008): 2657-2665. DOI.

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