Synthesis and characterization of oxorhenium(V)–‘3+1’ mixed thiolate [SNS]/[S] and [ONS]/[S] complexes. Crystal and molecular structures of [ReO(η3-SCH2C5H3NCH2S)(η1-C6H4Br-4-S)], [ReO(η3-SCH2C5H3NCH2O)(η1-C6H4X-4-S)] (X=Cl, OMe), [ReO(η3-SCH2C5H3NCH2O)(η1-C6H4OCH3-4-CH2S)] and [ReO(η3-SCH2C5H3NCH2S)(η1-C5H4NH-2-S)][Cl]

Abstract

The reaction of [ReOCl(3)(PPh(3))(2)] with the tridentate ligands 2,6-dithiomethylpyridine (4) or 6-thiomethyl-2-pyridinemethanol (5) and the appropriate monothiols, such as para-substituted benzenethiols (C(6)H(4)X-4-SH) (where X=F, Cl, Br and OCH(3)) and para-substituted benzylmercaptans (C(6)H(4)X-4-CH(2)SH) (where X=F, Cl and OCH(3)) in the presence of Et(3)N leads to the isolation of a series of integrated '3+1' oxorhenium(V) complexes. Similarly, reaction of [ReOCl(3)(PPh(3))(2)] with 2-mercaptopyridine and 4 afforded a cationic oxorhenium(V) complex, [ReO(eta(3)-SCH(2)C(5)H(3)NCH(2)S)(eta(1)-C(5)H(4)NH-2-S)][Cl] (22). Crystal data for 10, C(13)H(11)BrNOS(3)Re: triclinic, P1, a=7.2909(5), b=14.1978(9), c=15.991(1) A, alpha=77.184(1), beta=86.588(1), gamma=75.507(1) degrees , V=1562.69(18) A(3), Z=4. For 16, C(13)H(11)ClNO(2)S(2)Re: orthorhombic, P2(1)2(1)2(1), a=6.9728(6), b=13.477(1), c=15.761(1) A, V=1481.1(2) A(3), Z=4. For 18, C(14)H(14)NO(3)S(2)Re: monoclinic, P2(1)/c, a=15.6512(14), b=7.6678(7), c=13.732(1) A, beta=112.489(1) degrees , V=1522.7(2) A(3), Z=4. For 21, C(15)H(16)NO(3)S(2)Re: monoclinic, P2(1)/c, a=13.929(1), b=7.741(1), c=15.583(2) A, beta=103.600(2) degrees , V=1633.1(3) A(3), Z=4. For 22, C(12)H(11)ClN(2)OS(3)Re: monoclinic, C2(1)/(c), a=27.827(3), b=8.529(1), c=14.957(2) A, beta=119.314(2) degrees , V=3095.3(6) A(3), Z=8.

Exploring oxorhenium ‘3+1’ mixed-ligand complexes carrying the S-benzyl-3-[(2-hydroxyphenyl)methylene]dithiocarbazate [ONS]/monothiol [S] donor set: synthesis and characterization

“…The measurement uses the two largest angles contained in the mean basal plane, which expressed in the form (β−α)/ 60 give a unitless value ranging from 0 to 1 with τ=0 for perfect square pyramid, and τ=1 for ideal triagonal bipyramid. The τ value of 0.31 for 4 is higher than those reported previously in this laboratory in the investigation of [ONS]/[S] '3+1' complexes [11,12] …”

“…However, the stability of these '3+1' complexes is strongly dependent on small structural variations of the tridentate/monothiol ligand sets, especially of the tridentate ligands. [11] and 6-thiomethyl-2-pyridinemethanol [12]. The ReO 3+ core complexes of these ligands are characterized by an almost ideal square pyramidal configuration of the ReO 3+ core.…”

SNS-Ligands for Ru-Catalyzed Homogeneous Hydrogenation and Dehydrogenation Reactions

“…We started our investigations by preparing a variety of easily accessible SNS complexes II in analogy to Gusev’s work (Scheme ). In addition to these simple aliphatic ligand systems, we also decided to investigate pyridine-based SNS complexes III as well as the analogous SCS complexes IV . Besides these symmetric systems, we also synthesized a variety of dissymmetric S-containing pincer ligands to access the pyridine-based complexes V – VIII within this study …”

Synthesis and structural characterization of rhenium(I) tricarbonyl complexes with the bidentate ligands o-(diphenylphosphino)benzaldehyde (P∩O) and o-[(diphenylphosphino)benzylidene]analine (P∩N)

“…The inevitable formation of multiple isomers differing in their pharmacokinetics [10] aroused interest in developing an alternative '3+1' approach, in which a neutral oxometal complex in a distorted square pyramidal or trigonal bipyramidal molecular geometry was prepared by employing the mixed tridentate (SNS, ONS, ONO or SSS) ligand and mondentate thiol ligand with the appropriate MO 3+ precursors [11][12][13][14]. These '3+1' integrated complexes eliminated the possibility of syn and anti stereoisomers that are often produced in the tetradentate complexes, but they were found to be relatively unstable in vitro and in vivo due to metabolism and replacement of the monothiol ligand through transchelation by physiological thiols such as cysteine and glutathione [15].…”