Metallaheteroboranes with group 16 elements: Aspects of synthesis, framework and reactivity

Pathak, Kriti; Nandi, Chandan; Ghosh, Sundargopal

doi:10.1016/j.ccr.2021.214303

Cited by 18 publications

(14 citation statements)

References 151 publications

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“…In our earlier reports, we have effectually corroborated the efficacy of chalcogenated borohydrides such as Li[BH 3 EPh] (E = S, Se, or Te) as potential reagents for the synthesis of bimetallic chalcogen complexes in addition to dimetallaheteroboranes . In particular, the reactions of [(Cp*Ru) 2 (B 3 H 8 )(CS 2 H)] with Li[BH 3 SPh] and [Cp*IrCl 2 ] 2 with Li[BH 3 TePh] yielded bimetallic chalcogen-bridged half-sandwiched complexes .…”

Section: Introductionsupporting

confidence: 57%

Thiolate-Bridged Heterodinuclear Manganese–Cobalt Complexes with Bridging Hydride Ligands

et al. 2022

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Synthesis and structural elucidation of a series of thiolate-bridged heterobimetallic MnCo complexes are described. Irradiation of [Mn 2 (CO) 10 ] in the presence of Li[BH 3 SPh] followed by room-temperature reaction with [Cp*CoCl] 2 (Cp* = η 5 -C 5 Me 5 ) afforded dithiolate-and hydride-bridged dinuclear heterobimetallic MnCo complex [{(Mn(CO) 3 }(μ-SPh) 2 (μ-H){CoCp*}] (1). The solid-state structure of 1 established that the two metal fragments, {Mn(CO) 3 } and {Cp*Co}, are linked by a Mn−Co bond. In addition to 1, the reaction also yielded half-sandwiched trithiolate-bridged dinuclear MnCo complex [{Mn(CO) 3 }(μ-SPh) 3 (CoCp*)] (2) and a dinuclear heterometal-coordinated diborane analogue [{Mn(CO) 3 }(μ-η 2 :η 2 -SBH 3 )-(μ-H)(CoCp*)] (3). To isolate the Se analogues of 1−3, a similar reaction was carried out in the presence of Li[BH 3 SePh] that led to the formation of complexes [{(Mn(CO) 3 }(μ-SePh) 2 (μ-H)(CoCp*)] ( 4), [{Mn(CO) 3 }(μ-SePh) 3 (CoCp*)] ( 5), and [{Mn(CO) 3 }(μ-η 2 :η 2 -SeBH 3 )(μ-H)(CoCp*)] (6). All of the complexes were characterized by employing multinuclear nuclear magnetic resonance and infrared spectroscopies as well as mass spectrometric techniques. Single-crystal X-ray diffraction analyses of complexes 1, 2, and 4 helped to establish the molecular formulations and structural integrity of these complexes. The bonding interactions present in these di-or trichalcogenate-bridged dinuclear heterobimetallic complexes were explicated computationally by density functional theory calculations that supported the {Mn−H−Co} and Mn−Co bonding interactions in 1 and 4. The inherent electronic properties of all of the complexes were demonstrated by ultraviolet−visible spectroscopy. Furthermore, the critical involvement of the bridging chalcogenato functionalities was probed via cyclic voltammetry and complementary spectroelectrochemical studies.

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Section: Introductionsupporting

confidence: 57%

Thiolate-Bridged Heterodinuclear Manganese–Cobalt Complexes with Bridging Hydride Ligands

et al. 2022

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“…Apart from cluster fusion, several coordination compounds have been synthesized involving metal carbonyl fragments, chalcogens, boranes, and metallaboranes following the same way [ 44 , 45 , 46 ]. Beginning from the synthesis of [Pt(CS 2 )(PPh 3 ) 2 ], the first CS 2 metal complex by Wilkinson and co-workers, a range of CS 2 complexes containing transition metals have been synthesized [ 47 ].…”

Section: Introductionmentioning

confidence: 99%

Chemistry of CS2 and CS3 Bridged Decaborane Analogues: Regular Coordination Versus Cluster Expansion

et al. 2023

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In an effort to synthesize metallaheteroborane clusters of higher nuclearity, the reactivity of metallaheteroboranes, nido-[(Cp*M)2B6S2H4(CS3)] (Cp* = C5Me5) (1: M = Co; 2: M = Rh) with various metal carbonyls have been investigated. Photolysis of nido-1 and nido-2 with group 6 metal carbonyls, M’(CO)5.THF (M’ = Mo or W) were performed that led to the formation of a series of adducts [(Cp*M)2B6S2H4(CS3){M’(CO)5}] (3: M = Co, M’ = Mo; 4: M = Co, M’ = W; 5: M = Rh, M’ = Mo; 6: M = Rh, M’ = W) instead of cluster expansion reactions. In these adducts, the S atom of C=S group of di(thioboralane)thione {B2CS3} moiety is coordinated to M’(CO)5 (M = Mo or W) in η1-fashion. On the other hand, thermolysis of nido-1 with Ru3(CO)12 yielded one fused metallaheteroborane cluster [{Ru(CO)3}3S{Ru(CO)}{Ru(CO)2}Co2B6SH4(CH2S2){Ru(CO)3}2S], 7. This 20-vertex-fused cluster is composed of two tetrahedral {Ru3S} and {Ru2B2}, a flat butterfly {Ru3S} and one octadecahedron {Co2RuB7S} core with one missing vertex, coordinated to {Ru2SCH2S2} through two boron and one ruthenium atom. On the other hand, the room temperature reaction of nido-2 with Co2(CO)8 produced one 19-vertex fused metallaheteroborane cluster [(Cp*Rh)2B6H4S4{Co(CO)}2{Co(CO)2}2(μ-CO)S{Co(CO)3}2], 8. Cluster 8 contains one nido-decaborane {Rh2B6S2}, one butterfly {Co2S2} and one bicapped square pyramidal {Co6S} unit that exhibits an intercluster fusion with two sulfur atoms in common. Clusters 3–6 have been characterized by multinuclear NMR and IR spectroscopy, mass spectrometry and structurally determined by XRD analyses. Furthermore, the DFT calculations have been carried out to gain insight into electronic, structural and bonding patterns of the synthesized clusters.

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“…Owing to its electron-deficient character and having a delocalized bonding pattern, boron can form complex covalent clusters both with the main group and transition-metal elements . The synthesis and chemistry of boranes and their heteroatom derivatives like carboranes, metallaboranes, , metallacarboranes, and metallaheteroboranes cover a broad range of organometallic chemistry. The unique structures and novel bonding characteristics of such clusters are widely explored by many pioneers in this area. − The utilization of both electron counting rules and isolobal analogy has proven successful in connecting these boron clusters .…”

Section: Introductionmentioning

confidence: 99%

Degradation Chemistry of Dimetallaboranes, [(Cp*M)₂B₅H_9+x] with [Ph₂Se₂] (x = 2 or 0, M = V or Cr)

Haridas,

Chatterjee,

Giri

et al. 2023

Organometallics

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The synthesis and structural characterization of new divanadaborane clusters are reported. The pressure tube thermolysis of an intermediate formed by the reaction of [(Cp*VCl 2 ) 3 ] with [LiBH 4 •THF] and [BH 3 •THF] in diglyme at 160 °C yielded 6-sep, 7-vertex oblato-nido cluster, [(Cp*V) 2 B 5 H 11 ],2 (Cp* = pentamethyl-η 5 -cyclopentadienyl). In an attempt to test the reactivity of this cluster with chalcogenide ligands, thermolysis of 2 with [Ph 2 E 2 ] (E = S, Se, or Te) in toluene was carried out. While the reaction of 2 with [Ph 2 Se 2 ] resulted in the formation of [(Cp*V) 2 B 4 H 8 (SePh)(μ-SePh)], 3, via cluster degradation reaction, [Ph 2 S 2 ] and [Ph 2 Te 2 ] did not generate analogous clusters. Compound 3 is an example of a tetraborane cluster being stabilized by two SePh fragments, one bridging the two Cp*V fragments while the other forming a terminal bond with one of the boron atoms. In an attempt to explore the cluster degradation reaction with analogous group 6 metallaborane [(Cp*Cr) 2 B 5 H 9 ], 5, we treated it with [Ph 2 Se 2 ] that led to the formation of terminally substituted [(Cp*Cr) 2 B 5 H 7 (SePh) 2 ], 6. All the clusters were characterized by using various spectroscopic studies and X-ray diffraction analysis. Quantum chemical calculations using density functional theory methods were carried out to gain more insight into the bonding and electronic structure of 3 and 6.

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Metallaheteroboranes with group 16 elements: Aspects of synthesis, framework and reactivity

Cited by 18 publications

References 151 publications

Thiolate-Bridged Heterodinuclear Manganese–Cobalt Complexes with Bridging Hydride Ligands

Thiolate-Bridged Heterodinuclear Manganese–Cobalt Complexes with Bridging Hydride Ligands

Chemistry of CS2 and CS3 Bridged Decaborane Analogues: Regular Coordination Versus Cluster Expansion

Degradation Chemistry of Dimetallaboranes, [(Cp*M)₂B₅H_9+x] with [Ph₂Se₂] (x = 2 or 0, M = V or Cr)

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Metallaheteroboranes with group 16 elements: Aspects of synthesis, framework and reactivity

Cited by 18 publications

References 151 publications

Thiolate-Bridged Heterodinuclear Manganese–Cobalt Complexes with Bridging Hydride Ligands

Thiolate-Bridged Heterodinuclear Manganese–Cobalt Complexes with Bridging Hydride Ligands

Chemistry of CS2 and CS3 Bridged Decaborane Analogues: Regular Coordination Versus Cluster Expansion

Degradation Chemistry of Dimetallaboranes, [(Cp*M)2B5H9+x] with [Ph2Se2] (x = 2 or 0, M = V or Cr)

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Degradation Chemistry of Dimetallaboranes, [(Cp*M)₂B₅H_9+x] with [Ph₂Se₂] (x = 2 or 0, M = V or Cr)