title: Template Synthesis and Reactions of Tricarbonylmolybdenum Phosphadithiamacrocycle Complexes.
abstract: Treatment of [Me(4)N](2)[PhP(CH(2)CH(2)S)(2)] with [Mo(CO)(3)(NCMe)(3)] affords the reactive intermediate [Me(4)N](2)[Mo(CO)(3){PhP(CH(2)CH(2)S)(2)}] (1), which undergoes oxidation to afford [Mo{PhP(CH(2)CH(2)S)(2)}(2)] (2). Reaction of 1 with a variety of dichloroalkanes produces [Mo(CO)(3){c-PhP(CH(2)CH(2)S)(2)X}] (X = CH(2)CH(2), CH(2)CH(2)CH(2), CH(2)CHMe or CH(2)CH(OH)CH(2)). The structure of [Mo(CO)(3){c-PhP(CH(2)CH(2)S)(2)CH(2)CH(2)}] (3) has been established by X-ray crystallography and consists of a Mo(CO)(3) fragment facially coordinated by the tridentate c-PhP(CH(2)CH(2)S)(2)CH(2)CH(2) ligand. Reaction of 3 with bromine affords seven-coordinate [Mo(CO)(2){c-PhP(CH(2)CH(2)S)(2)CH(2)CH(2)}Br(2)] (7), the X-ray crystal structure of which reveals a carbonyl-capped octahedral geometry. Treatment of 3 with sulfur results in loss of the Mo(CO)(3) fragment and isolation of c-PhPS(CH(2)CH(2)S)(2)CH(2)CH(2) (8), the X-ray structure of which shows a nine-membered ring with the phosphorus center bearing phenyl and sulfide substituents. Reduction of 8 with sodium naphthalenide affords the parent ligand c-PhP(CH(2)CH(2)S)(2)CH(2)CH(2). Crystal data: 2, C(20)H(26)MoP(2)S(4), triclinic P&onemacr;, a = 8.105(3) Å, b = 8.263(3) Å, c = 17.663(4) Å, alpha = 100.29(2) degrees, beta = 99.78(2) degrees, gamma = 98.81(2) degrees, Z = 2; 3, C(15)H(17)MoO(3)PS(2), monoclinic P2(1)/n, a = 9.600(3) Å, b = 15.594(5) Å, c = 11.335(3) Å, beta = 93.01(2) degrees, Z = 4; 7, C(14)H(17)Br(2)MoO(2)PS(2), monoclinic P2(1)/c, a = 17.039(3) Å, b = 8.686(2) Å, c = 12.466(3) Å, beta = 100.52(2) degrees, Z = 4; 8, C(12)H(17)PS(3), monoclinic P2(1), a = 6.651(4) Å, b = 7.313(2) Å, c = 14.687(9) Å, beta = 101.62(3) degrees, Z = 2.
authors.affiliation: Department of Biosciences, University of Kent, Canterbury, Kent CT2 7NJ, U.K., Department of Inorganic Chemistry, The University of Bristol, Bristol BS8 1TS, U.K., Department of Chemistry and Biological Chemistry, University of Essex, Wivenhoe Park, Colchester CO4 3SQ, U.K., and Department of Chemistry, University of Kent, Canterbury, Kent CT2 7NH, U.K.
authors.forename: Philip J.
authors.initials: PJ
authors.lastname: Blower
authors.forename: John C.
authors.initials: JC
authors.lastname: Jeffery
authors.forename: John R.
authors.initials: JR
authors.lastname: Miller
authors.forename: Spencer N.
authors.initials: SN
authors.lastname: Salek
authors.forename: Dirk
authors.initials: D
authors.lastname: Schmaljohann
authors.forename: Raymond J.
authors.initials: RJ
authors.lastname: Smith
authors.forename: Michael J.
authors.initials: MJ
authors.lastname: Went