Template synthesis and reactions of tricarbonylmolybdenum phosphadithiamacrocycle complexes

Blower, Philip J. and Jeffery, John C. and Miller, John R. and Salek, Spencer N. and Schmaljohann, Dirk and Smith, Raymond J. and Went, Michael J. (1997) Template synthesis and reactions of tricarbonylmolybdenum phosphadithiamacrocycle complexes. Inorganic Chemistry, 36 (8). pp. 1578-1582. ISSN 0020-1669. (The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided)

The full text of this publication is not available from this repository. (Contact us about this Publication)


Treatment of [Me(4)N](2)[PhP(CH2CH2S)(2)] with [Mo(CO)(3)(NCMe)(3)] affords the reactive intermediate [Me(4)N](2)[Mo(CO)(3){PhP(CH2CH2S)(2)}] (1), which undergoes oxidation to afford [Mo{PhP(CH2CH2S)(2)}(2)] (2). Reaction of 1 with a variety of dichloroalkanes produces [Mo(CO)(3){c-PhP(CH2CH2S)(2)X}] (X = CH2CH2, CH2CH2CH2, CH(2)CHMe or CH2CH(OH)CH2). The structure of [Mo(CO)(3){c-PhP(CH2CH2S)(2)CH2CH2}] (3) has been established by X-ray crystallography and consists of a Mo(CO)(3) fragment facially coordinated by the tridentate c-PhP(CH2CH2S)(2)CH2CH2 ligand. Reaction of 3 with bromine affords seven-coordinate [Mo(CO)(2){c-PhP(CH2CH2S)(2)CH2CH2}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 is elation of c-PhPS(CH2CH2S)(2)CH2CH2 (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(CH2CH2S)(2)CH2CH2. Crystal data: 2, C20H26MoP2S4, triclinic P (1) over bar, a = 8.105(3) Angstrom, b = 8.263(3) Angstrom, c = 17.663(4) Angstrom, alpha = 100.29(2)degrees, beta = 99.78(2)degrees, gamma = 98.81(2)degrees, Z = 2; 3, C15H17MoO3PS2, monoclinic P2(1)/n, a = 9.600(3) Angstrom, b = 15.594(5) Angstrom, c = 11.335(3) Angstrom, beta = 93.01(2)degrees, Z = 4; 7, C14H17Br2MoO2PS2, monoclinic P2(1)/c, a = 17.039(3) Angstrom, b = 8.686(2) Angstrom, c = 12.466(3) Angstrom, beta = 100.52(2)degrees, Z = 4; 8, C12H17PS3, monoclinic P2(1), a = 6.651(4) Angstrom, b = 7.313(2) Angstrom, c = 14.687(9) Angstrom, beta = 101.62(3)degrees, Z = 2.

Item Type: Article
Depositing User: T. Nasir
Date Deposited: 29 Oct 2009 05:52
Last Modified: 09 Jun 2014 10:55
Resource URI: https://kar.kent.ac.uk/id/eprint/18298 (The current URI for this page, for reference purposes)
  • Depositors only (login required):