Thiolate Ligand Transfer from Metallothiolates to Phosphido-Bridged Heterobimetallic Compounds:  C−S Bond Cleavage in Benzenethiol and Formation of a Mixed-Metal Trinuclear Compound

Abstract

Thiolate ligand transfer occurred during the reaction between CpMo(CO) 3 SPh and CpW-(CO) 2 (µ-PPh 2 )Mo(CO) 5 ( 1) in dichloromethane at reflux, resulting in the new mixed-metal and mixed-ligand bridged compound CpW(CO)(µ-SPh) 2 (µ-PPh 2 )Mo(CO) 3 (2). However, when CpW(CO) 3 SPh reacted with 1 under similar conditions, 2 and the mixed-metal trinuclear compound CpW(CO)(µ-S) 2 (µ-PPh 2 )Mo(CO) 2 (µ-PPh 2 )W(CO) 2 Cp (4) were formed. The presence of the (µ-S) 2 bridges in 4 indicates C-S bond cleavage in the SPh ligand. Reflux of a dichloromethane solution of 1 and PhSH also produced 2 along with CpW(CO)(µ-SPh) 2 (µ-PPh 2 )Mo(CO)(SPh) 2 (3) and CpW(CO)(µ-SPh) 2 (µ-PPh 2 )Mo(CO) 2 (PPh 2 H) (5). Moreover, the same reactants in benzene at reflux gave 2, 3, 5, and the additional product CpW(CO)(µ-SPh) 2 (µ-PPh 2 )Mo(CO) 2 (PPh 3 ) (6). The reaction of 1 with Ph 2 S 2 in dichloromethane at reflux produced compounds 2 and 3. Similarly conducted reactions in benzene at reflux afforded 2, 3, and 6. Compounds 2-6 were characterized by single-crystal X-ray diffraction analyses. Formation of the PPh 3 ligand, which coordinated to 6, suggests C-S bond cleavage in PhSH and Ph 2 S 2. Compounds 3, 5, and 6 were also synthesized in high yield by refluxing 2 with PhSH or Ph 2 S 2 , PPh 2 H, and PPh 3 , respectively, in benzene.

C–S bond cleavage in pyridylmethylthioether systems promoted by oxorhenium(V) ion

“…Several examples of C-S bond cleavage within organic molecules by different metal ions [16][17][18][19][20][21] were reported, considering the fundamental urgency of this aspect. To the best of our knowledge, there are reports of C-S bond cleavage within oxorhenium(V) complexes of organic moiety comprising C-S fragment [19][20][21] and within thiophenes by Re 2 (CO) 10 through hydrogenation, [22] but the present results are unprecedented. In fact we have found that the reaction under mild conditions between oxorhenium(V) ion and pyridylthioether systems cleaves C-S bond selectively, giving thiolato oxorhenium(V) products, although earlier reports showed that the C-S bond in 1,2-bis(2-pyridylmethylthio)ethane (BPT 1 ) and 1,3-bis(2-pyridylmethylthio)propane (BPT 2 ), and in similar type of organic compounds having N,S donor environment is quite stable towards hydrolysis in the presence of transition metal ions and different metal complexes have been reported so far [23][24][25][26][27][28][29][30][31][32][33][34][35][36][37].…”

“…But in hydrated alcoholic medium no C-S bond cleavage induced by ReO(V) ion occurred in any of the BPT systems rather the conversion of ReO(V) into perrhenate salt was observed; this reaction mixture, in turn on reaction with copper(II) nitrate trihydrate salt, produce [Cu(BPT)Cl]ReO 4 (2) type complexes. The solidstate structures of complexes 1a and 2a were established by X-ray crystallography.Ó 2009 Elsevier B.V. All rights reserved.The transition-metal-mediated cleavage of a C-S bond has been paid considerable attention due to its importance in synthetic chemistry, [1-3] petrochemical hydrodesulfurization, [4][5][6][7][8][9][10][11] biorganic and bioinorganic chemistry [12][13][14][15]. Several examples of C-S bond cleavage within organic molecules by different metal ions [16][17][18][19][20][21] were reported, considering the fundamental urgency of this aspect.…”

Cyclopentadienyl tungsten complexes with thiocarboxylate and thiosulfonate ligands: Structures of CpW(CO)3SCOPh and CpW(CO)3SSO2-4-C6H4Cl

“…Organotungsten complexes supported by sulfur-donor ligands have attracted continuous interest in recent years [1][2][3][4]. The thiolato complexes CpW(CO) 2 (L)SR (L = CO, PPh 3 ) are accessible by several routes [5][6][7][8][9][10].…”

A novel ligand transfer reaction: Transferring an N3-donor amine ligand from Ni(II) to Cu(II)—structural, spectral, theoretical, and docking studies

“…Studies on coordination modes of the organosulfur compounds and their transformations on bimetallic complexes and clusters are informative in gaining insights into the hydrodesulfurization (HDS) process (a catalytic process that is used to remove sulfur from organosulfur compounds in fossil fuel feedstocks). 13 These types of reactions have been employed for the synthesis of chiral complexes. 1 It is known that the catalytic activity of metals involves the mobility of species chemisorbed on metallic surfaces or the transfer of ligands between metal atoms, 14 thus ligand-transferring complexes may be a good choice for catalytically active compounds.…”