Synthetic and structural investigations of linear and macrocyclic nickel/iron/sulfur cluster complexes.
Three series of new Ni/Fe/S cluster complexes have been prepared and structurally characterized. One series of such complexes includes the linear type of (diphosphine)Ni-bridged double-butterfly Fe/S complexes [(μ-RS)(μ-S═CS)Fe(2)(CO)(6)](2)[Ni(diphosphine)] (1-6; R = Et, t-Bu, n-Bu, Ph; diphosphine = dppv, dppe, dppb), which were prepared by reactions of monoanions [(μ-RS)(μ-CO)Fe(2)(CO)(6)](-) (generated in situ from Fe(3)(CO)(12), Et(3)N, and RSH) with excess CS(2), followed by treatment of the resulting monoanions [(μ-RS)(μ-S═CS)Fe(2)(CO)(6)](-)with (diphosphine)NiCl(2). The second series consists of the macrocyclic type of (diphosphine)Ni-bridged double-butterfly Fe/S complexes [μ-S(CH(2))(4)S-μ][(μ-S═CS)Fe(2)(CO)(6)](2)[Ni(diphosphine)] (7-9; diphosphine = dppv, dppe, dppb), which were produced by the reaction of dianion [{μ-S(CH(2))(4)S-μ}{(μ-CO)Fe(2)(CO)(6)}(2)](2-) (formed in situ from Fe(3)(CO)(12), Et(3)N, and dithiol HS(CH(2))(4)SH with excess CS(2), followed by treatment of the resulting dianion [{μ-S(CH(2))(4)S-μ}{(μ-S═CS)Fe(2)(CO)(6)}(2)](2-) with (diphosphine)NiCl(2). However, more interestingly, when dithiol HS(CH(2))(4)SH (used for the production of 7-9) was replaced by HS(CH(2))(3)SH (a dithiol with a shorter carbon chain), the sequential reactions afforded another type of macrocyclic Ni/Fe/S complex, namely, the (diphosphine)Ni-bridged quadruple-butterfly Fe/S complexes [{μ-S(CH(2))(3)S-μ}{(μ-S═CS)Fe(2)(CO)(6)}(2)](2)[Ni(diphosphine)](2) (10-12; diphosphine = dppv, dppe, dppb). While a possible pathway for the production of the two types of novel metallomacrocycles 7-12 is suggested, all of the new complexes 1-12 were characterized by elemental analysis and spectroscopy and some of them by X-ray crystallography.
Song
Li-Cheng
LC
Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China. lcsong@nankai.edu.cn
Li
Yu-Long
YL
Li
Ling
L
Gu
Zhen-Chao
ZC
Hu
Qing-Mei
QM
D018360:Crystallography, X-Ray; D007501:Iron / Q000737:chemistry*; D047028:Macrocyclic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*
D047028:Macrocyclic Compounds; D009942:Organometallic Compounds; D013455:Sulfur; D009532:Nickel; D007501:Iron