Planar triple-decker and capped octahedral clusters of group-6 transition metals

Bag, Ranjit; Gayen, Sourav; Mohapatra, Stutee; Antharjanam, P. K. Sudhadevi; Halet, Jean‐François; Ghosh, Sundargopal

doi:10.1016/j.jorganchem.2021.122023

Cited by 3 publications

(6 citation statements)

References 66 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As shown in Figure , the crystal structure of 6 can be described as a heterometallic boride cluster having a boron atom placed at a semi-interstitial position of the butterfly M 2 M′ 2 core (M= Mo, M′ = Co). The observed Mo–B (2.41 Å) and Co–B (2.05 Å) bond distances are consistent with the known molybdaboranes, cobaltaboranes, and other reported μ 4 -boride clusters. ,, The boron atom is situated at a semi-interstitial position in quite bent fashion because of the Mo1–B1–Mo2 angle of 163.7°. Cluster 6 comprises of 62 CVE, and it is isostructural as well as isoelectronic to recently reported [{Cp*W(CO) 2 } 2 {Co 2 (CO) 5 }(μ 4 -B)(μ 2 -H)]…”

Section: Resultssupporting

confidence: 86%

Structures and Bonding of Early Transition Metallaborane Clusters

et al. 2022

Self Cite

View full text Add to dashboard Cite

Structures and bonding of various homo and heterometallic metallaborane clusters are described which are stabilized in the coordination sphere of early transition metals. For example, the bimetallic triborane species, [{Cp*Mo(CO)}2{µη 3 :η 3 -B3H7}], 2 has been synthesized from the pyrolysis of an in situ generated intermediate, produced from the reaction of [Cp*Mo(CO)3Me], 1 and [LiBH4•THF], with an excess amount of [BH3•THF]. Superficially cluster 2 is isostructural but not isoelectronic with [(Cp*MoCl)2B3H7] (I). Both clusters 2 and I contain a bimetallic template bridged by {B3H7} moiety. Cluster 2 is denoted as a unique saturated and unsubstituted closo bimetallic B3H7 cluster. Theoretical output implies that saturation in such clusters brings thermodynamic stability. Further, we have developed a new strategy for the synthesis of various heterometallic metal-rich metallaborane clusters. For example, pyrolysis of an intermediate, obtained from the reaction of [Cp*MoCl4], 4 and [LiBH4•THF], with cobalt and iron carbonyl compounds yielded triply bridging hydrido(hydroborylene), [{Cp*Mo(CO)2}2Co(CO)3BH(μ-H)], 5, tetrametallic μ4-boride, [{Cp*Mo(CO)2}2(μ4-B)(μ-H){Co2(CO)5}], 6, triple decker complex, [(Cp*Mo)2{µ-η 6 :η 6 -B4H4Co2(CO)5}(μ-H)2], 7, metal-rich dimolybdaborane cluster, [(Cp*Mo)2Co2(CO)3(μ-CO)3B3H3(μ-H)2], 8 and mixed-metal cluster, [(Cp*Mo)2B4H8Fe(CO)3], 9. All the molecules have been characterized by 1 H, 11 B{ 1 H}, and 13 C{ 1 H} NMR spectroscopy; mass spectrometry; infrared (IR) spectroscopy and single-crystal X-ray diffraction studies for clusters 2 and 5-9. The electron counting rules and density functional theory (DFT) calculations provided further insight into the bonding and electronic structures of these clusters.

show abstract

Section: Resultssupporting

confidence: 86%

Structures and Bonding of Early Transition Metallaborane Clusters

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…Although several triple-decker complexes containing homocyclic rings composed of phosphorus, arsenic, carbon and boron as middle decks are known in the literature, [8,13,15,16,36] heterocyclic ring systems comprised of metal atoms in middle decks are still limited. [61][62][63][64] In1999, Fehlner group first reported the synthesis of a triple-decker complex having boron and metal in the middle deck, [(Cp*Re) 2 {μ-η 6 :η 6 -B 4 H 4 Co 2 (CO) 5 }] ( 61). [61] The reaction of 1 with [Co 2 (CO) 8), whereas BÀ Co bonds are in the range of reported cobaltaborane clusters.…”

Section: Complexes Comprising Boron and Metal Atoms In The Middle Deckmentioning

confidence: 99%

“…Our subsequent efforts succeeded in 2015, when we reported [(Cp*Mo) 2 {μ-η 6 :η 6 -B 4 H 4 Ru 2 (CO) 6 }] (63) which is a rare example of a triple-decker complex with 22 valence electrons [2×11 {Cp*Mo} + 1×0 {B 4 H 4 Ru 2 (CO) 6 } = 22]. [61][62][63][64] Complex 63 featured a [B 4 Ru 2 ] ring in the middle deck. [62] This was achieved synthetically by exploiting the reaction of [Ru 3 (CO However, to confirm the exact structure single crystal X-ray diffraction analysis of 63 was performed using suitable crystals which disclosed the triple-decker structure of the molecule in which a hexagonal [B 4 H 4 Ru 2 (CO) 6 ] ring was sandwiched between two {Cp*Mo} fragments.…”

Section: Complexes Comprising Boron and Metal Atoms In The Middle Deckmentioning

confidence: 99%

“…Recently, based on the multinuclear spectroscopy and X-ray diffraction analysis, we have isolated a triple-decker complex [(Cp*Mo) 2 {μη 6 :η 6 -B 4 H 4 Co 2 (CO) 5 }(H) 2 ], 65, analogous to 64. [64] These compounds can be identified as unprecedented examples of tripledecker complexes comprising bridging hydrogens. In parallel, the geometries of 64 and 65 can also be viewed as the oblatocloso-hexagonal bipyramid with six skeletal electron pairs (sep), which is in agreement with (n-2) sep for such structural type, similar to that of reported triple-decker complexes.…”

Section: Complexes Comprising Boron and Metal Atoms In The Middle Deckmentioning

confidence: 99%

See 1 more Smart Citation

Transition Metal Triple‐decker Sandwich Complexes Containing Group 13 Elements

Chatterjee,

Bairagi,

Ghosh

2023

Chemistry An Asian Journal

Self Cite

View full text Add to dashboard Cite

Transition metal triple‐decker complexes are an interesting class of sandwich complexes that engrossed great attention due to their structures and properties. Over the decades, synthesis of triple‐decker complexes featuring homocyclic, heterocyclic or π‐conjugated rings as middle decks have been abundantly reported. In this regard, the chemistry of such complexes bearing boron in the middle deck are well explored due to the ability of boron‐containing cycles to readily coordinate bifacially with metal atoms thereby forming triple‐decker complexes. On the other hand, electron counting rules and theoretical calculations have strengthened our knowledge of the structure and bonding in these complexes. Further, these complexes can be used as synthons to generate organometallic polymers having interesting electronic, optical and magnetic properties that can be appropriately tuned to cater to a wide range of applications. In our quest for novel metallaboranes and metallaheteroboranes, we have been successful in isolating various triple‐decker complexes that feature boron in the middle deck. This review explained elaborately the synthesis, structures, and bonding in such complexes reported by us and others.

show abstract

“…12 Half-sandwich complexes of platinum group metals (Ir, Rh, Ru and Os) and certain recent biological and catalytic applications of these complexes have been recently reported. 20 Triple-decker sandwiches containing planar {B 2 E 2 Pd} rings ( E = S or Se) were studied by Joseph et al 21 Planar triple-decker and capped octahedral clusters of group-6 transition metals were studied by Bag et al 22 Gao et al performed a theoretical study on sandwich-like transition-metal–cyclooctatetraene clusters and one-dimensional infinite molecular wires. 23 The electronic properties of transition metal–benzene sandwich clusters have been well documented.…”

Section: Introductionmentioning

confidence: 99%