Reactions of rhenium and manganese carbonyl complexes with 1,8-bis(diphenylphosphino)naphthalene: Ligand chelation, C–H and C–P bond-cleavage reactions

Reaction of [Re2(CO)8(MeCN)2] with 1,8-bis(diphenylphosphino)naphthalene (dppn) afforded three mono-rhenium complexes fac-[Re(CO)3(κ1:η1-PPh2C10H6)(PPh2H)] (1), fac-[Re(CO)3{κ1:κ1:η1-(O)PPh2C10H6(O)PPh(C6H4)}] (2) and fac-[ReCl(CO)3(κ2-PPh2C10H6PPh2)] (3). Compounds 1–3 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 κ1:κ1:η1-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)3(κ2-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)9{κ1-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 1–3, 5, 6 are reported.

Graphical abstractReactions of [Re2(CO)8(MeCN)2] and [Mn2(CO)8(MeCN)2] with 1,8-bis (diphenylphosphino)naphthalene (dppn) are described. Treatment of [Re2(CO)8(MeCN)2] with dppn furnished three mono-rhenium complexes fac-[Re(CO)3(κ1:η1-PPh2C10H6)(PPh2H)] (1), fac-[Re(CO)3{κ1:κ1:η1-(O)PPh2C10H6(O)PPh(C6H4)}] (2) and fac-[ReCl(CO)3(PPh2C10H6PPh2)] whereas two dinuclear compounds [Mn2(CO)8(κ-PPh2)2] (4) and [Mn2(CO)9{κ1-PPh2(C10H7)}] (6) and the mononuclear fac-[MnCl(CO)3(PPh2C10H6PPh2)] (5) were obtained from the [Mn2(CO)8(MeCN)2] with dppn.Figure optionsDownload full-size imageDownload as PowerPoint slide