187961-06-4Relevant academic research and scientific papers
Template Synthesis and Reactions of Tricarbonylmolybdenum Phosphadithiamacrocycle Complexes
Blower, Philip J.,Jeffery, John C.,Miller, John R.,Salek, Spencer N.,Schmaljohann, Dirk,Smith, Raymond J.,Went, Michael J.
, p. 1578 - 1582 (1997)
Treatment of [Me4N]2[PhP(CH2CH2S)2] with [Mo(CO)3(NCMe)3] affords the reactive intermediate [Me4N]2[Mo(CO)3{PhP(CH2CH 2S)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)2X)] (X = CH2CH2, CH2CH2CH2, CH2CHMe or CH2CH(OH)CH2). The structure of [Mo(CO)3{c-PhP(CH2CH2S)2CH 2CH2}] (3) has been established by X-ray crystallography and consists of a Mo(CO)3 fragment facially coordinated by the tridentate c-PhP(CH2CH2S)2CH2CH2 ligand. Reaction of 3 with bromine affords seven-coordinate [Mo(CO)2{c-PhP(CH2-CH2S)2CH 2CH2]Br2] (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(CH2CH2S)2CH2CH2 (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)2CH2-CH2. Crystal data: 2, C20H26MoP2S4, triclinic P1, a = 8.105(3) ?, b = 8.263(3) ?, c = 17.663(4) ?, a = 100.29(2)°, β = 99.78(2)°, γ = 98.81(2)°, Z = 2; 3, C15H17MoO3PS2, monoclinic P21/n, a = 9.600(3) ?, b = 15.594(5) ?, c = 11.335(3) ?, β = 93.01(2)°, Z = 4; 7, C14H17Br2MoO2PS2, monoclinic P21/c, a = 17.039(3) ?, b = 8.686(2) ?, c = 12.466(3) ?, β = 100.52(2)°, Z = 4; 8, C12H17PS3, monoclinic P21, a = 6.651(4) ?, b = 7.313(2) ?, c = 14.687(9) ?, β= 101.62(3)°, Z = 2.
