Centrosymmetric [Mn2(CO)6(μ-thpymS)2] (thpymS = tetrahydropyrimidine-2-thionato) as a synthon to mixed-metal clusters

Diphosphine-induced thiolate-bridge scission of [Re(CO)3(μ,κ2-S,N-thpymS)]2 (thpymS = 1,4,5,6-tetrahydropyrimidine-2-thiolate): Structural and computational studies of configurational isomers of [Re(CO)3(κ2-S,N-thpymS)]2(μ,κ1,κ1-dppe)

“…A long-term research theme within our laboratories has involved the reactivity investigation of transition metal carbonyls with heterocyclic thiols, and our results have revealed that the outcomes of these reactions are influenced by both the intrinsic reactivity of the metal carbonyl substrate and the structure of the initial heterocyclic thiol . For example, reactions between M 2 (CO) 10 (M = Mn, Re) and pyrimidine-2-thiol (pymSH) furnish tetranuclear "square-type" clusters [M(CO) 3 (µ,κ 2 -S,N-pymS)] 4 [28], while similar reactions with tetrahydropyrimidine-2-thiol (thpymSH) or pyridine-2-thiol (pySH) affords only dinuclear products [M(CO) 3 (µ,κ 2 -S,N-thpymS)] 2 [29,34] and [M(CO) 3 (µ,κ 2 -S,N-pyS)] 2 [5,22,42], respectively. Further, structural analyses reveal that while In comparison to the extensive number of reports published for this genre of dinuclear complexes that adopt a chiral structure, very little attention has been paid to dinuclear complexes that adopt a centrosymmetric structure [29,34].…”

“…For example, reactions between M 2 (CO) 10 (M = Mn, Re) and pyrimidine-2-thiol (pymSH) furnish tetranuclear "square-type" clusters [M(CO) 3 (µ,κ 2 -S,N-pymS)] 4 [28], while similar reactions with tetrahydropyrimidine-2-thiol (thpymSH) or pyridine-2-thiol (pySH) affords only dinuclear products [M(CO) 3 (µ,κ 2 -S,N-thpymS)] 2 [29,34] and [M(CO) 3 (µ,κ 2 -S,N-pyS)] 2 [5,22,42], respectively. Further, structural analyses reveal that while In comparison to the extensive number of reports published for this genre of dinuclear complexes that adopt a chiral structure, very little attention has been paid to dinuclear complexes that adopt a centrosymmetric structure [29,34]. In a continuation of our previous work, we now report on the reactivity of [Re(CO) 3 (µ,κ 2 -S,N-thpymS)] 2 (1) with the diphosphines, bis(diphenylphosphino)methane (dppm) and 1,2-bis(diphenylphosphino)ethane (dppe).…”

Investigation on the reactivity of tetranuclear Group 7/8 mixed-metal clusters toward triphenylphosphine

“…Heterometallic systems may also combine the catalytic features of different metals to give novel reactivity that is inaccessible by homometallic systems [7]. We have reported systematic synthesis of a number of mixed-metal carbonyl clusters containing heterocyclic thiolate ligand(s) in the past few years [8][9][10][11][12][13][14][15][16]. For example, the Group 7/8 mixed-metal clusters of the general formula MM′3(CO)13(µ3-L) [M = Mn, Re; M′ = Os, Ru;…”

“…L-H = nitrogen containing heterocyclic thiol] can be readily obtained from the direct reaction between M′3(CO) x (x = 0, 2) and M2(CO)6(µ-L)2 in moderate to good yield (Scheme 1). The metallic core of these mixed-metal clusters forms a butterfly skeleton where the Group 7 metal (Mn or Re) always occupies a wingtip position [10][11][12][13][14][15][16]. The heterocyclic thiolate ligand is facially located on the convex side of the butterfly core that contains the Group 7 metal, but recent studies showed that it can also be shifted to the other face of the convex side by heating as shown in Scheme 1 [16].…”

Reactivity of [M4(co)12(µ-pyms)4] (M = Mn, re; pymS = pyrimidine-2-Thiolate) with bis(triphenylphosphino)nickel(ii) dicarbonyl: X-ray crystal structure of [Re(Co)3(?2-pymS)(PPh3)]

“…The reactions of M 2 (CO) 10 (M = Re, Mn) with pySH at 25 o C in the presence of Me 3 NO gave dinuclear pyridine-2-thiolate complexes [M 2 (CO) 6 (-pyS) 2 ], while that of with pymSH afforded the tetranuclear pyrimidine-2-thiolato complexes [Mn 4 (CO) 12 (-pymS) 4 ]. These complexes serve as versatile precursors for mononuclear complexes of the general formula [M(CO) 3 (µ-L)] n (M = Mn, Re; L = heterocyclic-thiolate; n = 2, 4) (Islam et al 1999, Ara et al 2003, 2011, 2012 (Rahman et al 2012). …”