• Bairagi, Subhash
• Pradhan, Alaka Nanda
• Cordier, Marie
• Roisnel, Thierry

Abstract

<jats:title>Abstract</jats:title><jats:p>Synthesis, bonding and chemistry of mono‐ and bimetallic complexes supported by chelating thiolato ligands have been established. Treatment of [Cp*VCl<jats:sub>2</jats:sub>]<jats:sub>3</jats:sub> (<jats:bold>1</jats:bold>) with [LiBH<jats:sub>4</jats:sub> ⋅ THF] followed by the addition of ethane‐1,2‐dithiol led to the formation of an EPR active bimetallic vanadium thiolato complex [(Cp*V){<jats:italic>μ</jats:italic>‐(SCH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>S)‐<jats:italic>κ</jats:italic><jats:sup>2</jats:sup>S,S′)<jats:sub>2</jats:sub>{V(SCH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>S‐SH)}] (<jats:bold>2</jats:bold>). In complex <jats:bold>2</jats:bold>, two ethane‐1,2‐dithiolato ligands are symmetrically coordinated to two vanadium atoms through <jats:italic>μ</jats:italic>‐S atoms. Interestingly, when similar reactions were carried out with heavier group 5 metal precursors, such as [Cp*NbCl<jats:sub>4</jats:sub>] (<jats:bold>3 a</jats:bold>), it afforded monometallic thiolato complex [Cp*Nb(SCH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>S)(SCH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>S−CH<jats:sub>2</jats:sub>S)] (<jats:bold>4 a</jats:bold>). On the other hand, the Ta‐analogue [Cp*TaCl<jats:sub>4</jats:sub>] (<jats:bold>3 b</jats:bold>) yielded thiolato species [Cp*Ta(SCH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>S)(SCH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>S−CH<jats:sub>2</jats:sub>S)] (<jats:bold>4 b</jats:bold>) and [Cp*Ta(SCH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>S) (SCH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>S−S)] (<jats:bold>5</jats:bold>). In complexes <jats:bold>4 a</jats:bold> and <jats:bold>4 b</jats:bold>, one ethane‐1,2‐dithiolato and one trithiolato ligand are coordinated to Nb and Ta centers, respectively. Whereas, in complex <jats:bold>5</jats:bold>, one ethane‐1,2‐dithiolato and one 2‐disulfanylethanethiolato is coordinated to the Ta center. Moreover, the photolytic reaction of <jats:bold>5</jats:bold> with [Mo(CO)<jats:sub>5</jats:sub> ⋅ THF] yielded heterobimetallic thiolato complex [(Cp*Ta){<jats:italic>μ</jats:italic>‐(SCH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>S)‐<jats:italic>κ</jats:italic><jats:sup>2</jats:sup>S,S′}{<jats:italic>μ</jats:italic>‐(SCH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>S−CH<jats:sub>2</jats:sub>(CH<jats:sub>3</jats:sub>)S)<jats:italic>κ</jats:italic><jats:sup>2</jats:sup>S′′ : <jats:italic>κ</jats:italic><jats:sup>1</jats:sup>S‐′′′′ : <jats:italic>κ</jats:italic><jats:sup>1</jats:sup>S′′′′′}{Mo(CO)<jats:sub>3</jats:sub>}] (<jats:bold>6</jats:bold>). All the complexes have been characterized by multinuclear NMR spectroscopy and single crystal X‐ray diffraction studies. Further, computational analyses were performed to provide an insight into the bonding of these complexes.</jats:p>

Topics

• impedance spectroscopy
• single crystal
• electron spin resonance spectroscopy
• Nuclear Magnetic Resonance spectroscopy
• vanadium