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)

Abstract

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Alkyl 2-Benzothiazolyl Sulfide Ligated Dirhenium Complexes: Syntheses, Structure and Computational Study of [Re2(CO)8{μ,η1,η1-(R)SCNSC6H4}] (R = CH3 and C2H5)

“…The rhenium-rhenium bond distance in compounds 1 and 2 are in the comparable range, The Re atoms of the compounds are in the octahedral coordination sphere, but the bond angles about the Re cores suggest there is a profound distortion from the ideal octahedral geometry. The observed N1─Re1─Re2 and S1─Re2─Re1 bond angles in compound 1 are 84.83 (9) and 77.29(3)°, respectively, which is due to the rigid structure of the ligating 2- The Hirshfeld surface of compound 1 was generated with the surface mapped over a fixed color scale of -0.1319 Å (red) to 1.2641 Å (blue) and for compound 2 -0.4436 Å (red) to 1.4136 Å (blue). The red circular spots over the Hirshfeld surface indicate the strong O---H and C---H hydrogen bond interactions (Figures 4a and 4b).…”

“…For example, the reactions of Re2(CO)10 with pyridine-2-thiol [1], thioacetamide [2], thiobenzamide [2], diaryl disulfides [3], pyrimidine-2-thiol [4], 2-mercaptothiazoline [5], 2mercaptobenzimidazole [5], 2-mercapto-1-methylimidazole [5], and 2-mercaptobenzoxazole [6] have been reported. Recent advances in research reveal the isolation of mixed metal [7][8][9] and mixed ligand [10][11][12][13] rhenium complexes of sulfur-containing ligands. These reactions often involve the oxidative cleavage of the rhenium-rhenium bond together with the reductive S─H, N─H or S─S bond scission in the ligands [1][2][3][4][5][6].…”

The chemistry of rhenium and manganese carbonyl complexes bearing heterocyclic thiolate ligands: Mono‒, di‒, tri‒, and tetranuclear complexes

“…The solid-state structure determination shows that in 48, the pyrimidine-2-thiolate ligand binds in a chelating fashion. Rigid dppm reacts with 44 to give [Re(CO)3(κ 1 -dppm)(κ 2 -thpymS)] ( 50) resulting from phosphine-promoted scission of the dithiolate bridges (Moni et al, 2018). When 50 is heated in toluene at 110 o C, CO is lost, and dinuclear [Re2(CO)4(µ-dppm)(µ,κ 2 -thpymS)2] (51) is formed (Scheme 9), which has two thiolates and one dppm ligand bridging Re-Re bond.…”