Reactivity of Diruthenium and Dirhodium Analogues of Pentaborane(9): Agostic versus Boratrane Complexes

Anju, R. S.; Roy, Dipak Kumar; Mondal, Bijan; Yuvaraj, K.; Arivazhagan, C.; Saha, Koushik; Varghese, Babu; Ghosh, Sundargopal

doi:10.1002/ange.201310416

Cited by 27 publications

(8 citation statements)

References 48 publications

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“…Experimentally, the formation of an agostic bond is distinguished first and foremost by an activation of the s bond interacting with the metallic center. 86 In the same chemical family of compounds, it may be possible to qualitatively estimate the agostic character of the bonding, by comparing their reactivity toward a same reagent. On the other hand, such a qualitative approach will be limited to a specific chemical family of compounds and may depend on the reagents.…”

Section: A Qualitative Comparison Of Different Agostic Bondsmentioning

confidence: 99%

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Activation of C–H and B–H bonds through agostic bonding: an ELF/QTAIM insight

Zins

Silvi

Alikhani

2015

Phys. Chem. Chem. Phys.

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Agostic bonding is of paramount importance in C-H bond activation processes. The reactivity of the σ C-H bond thus activated will depend on the nature of the metallic center, the nature of the ligand involved in the interaction and co-ligands, as well as on geometric parameters. Because of their importance in organometallic chemistry, a qualitative classification of agostic bonding could be very much helpful. Herein we propose descriptors of the agostic character of bonding based on the electron localization function (ELF) and Quantum Theory of Atoms in Molecules (QTAIM) topological analysis. A set of 31 metallic complexes taken, or derived, from the literature was chosen to illustrate our methodology. First, some criteria should prove that an interaction between a metallic center and a σ X-H bond can indeed be described as "agostic" bonding. Then, the contribution of the metallic center in the protonated agostic basin, in the ELF topological description, may be used to evaluate the agostic character of bonding. A σ X-H bond is in agostic interaction with a metal center when the protonated X-H basin is a trisynaptic basin with a metal contribution strictly larger than the numerical uncertainty, i.e. 0.01 e. In addition, it was shown that the weakening of the electron density at the X-Hagostic bond critical point with respect to that of X-Hfree well correlates with the lengthening of the agostic X-H bond distance as well as with the shift of the vibrational frequency associated with the νX-H stretching mode. Furthermore, the use of a normalized parameter that takes into account the total population of the protonated basin, allows the comparison of the agostic character of bonding involved in different complexes.

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Section: A Qualitative Comparison Of Different Agostic Bondsmentioning

confidence: 99%

“…In a first Change in the reactivity. 14,86 The reactivity will obviously depend on co-ligands, geometry and the exact chemical nature of agostic bonding. NMR spectra cannot be obtained for dynamical systems.…”

Section: Doðhàxþ Oðhàxþ Free Ligandmentioning

confidence: 99%

Activation of C–H and B–H bonds through agostic bonding: an ELF/QTAIM insight

Zins

Silvi

Alikhani

2015

Phys. Chem. Chem. Phys.

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“…[17,18] As part of our ongoing studies on the synthesis of electronprecise transition-metal-boron complexes from metallaboranes, [19,20] we have recently reported several s-borate/B-agostic complexes from the reaction of [(Cp*Ru) 2 B 3 H 9 ]w ith the 2mercaptobenzothiazolyl (mbz) ligand (Cp* = h 5 -C 5 Me 5 ). [21] Alternatively, we have shown that these complexes can also be generated from the reaction of [Cp*MCl 2 ] 2 (M = Ru, Rh, or Ir) with Na[H 2 B(mbz) 2 ]. [22] Subsequently,w ei solated various sborane/borate group 6c omplexes from the reaction of [Cp*Mo(CO) 3 Me] and [BH 3 ·EPh]Li (E = S, Se, or Te).…”

Section: Introductionmentioning

confidence: 99%

Design, Synthesis, and Chemistry of Bis(σ)borate and Agostic Complexes of Group 7 Metals

Saha

Ramalakshmi

Gomosta

et al. 2017

Chemistry A European J

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A series of new bis(σ)borate and agostic complexes of group 7 metals have been synthesized and structurally characterized from various borate ligands, such as trihydrobis(benzothiazol-2-yl)amideborate (Na[(H B)bbza]), trihydro(2-aminobenzothiazolyl)borate (Na[(H B)abz]), and dihydrobis(2-mercaptopyridyl)borate (Na[(H B)mp ]) (bbza=bis(benzothiazol-2-yl)amine, abz=2-aminobenzothiazolyl, and mp=2-mercaptopyridyl). Photolysis of [Mn (CO) ] with Na[(H B)bbza] formed bis(σ)borate complex [Mn(CO) (μ-H) BHNCSC H (NR)] (1; R=NCSC H ). Octahedral complex [Re(CO) (N C S C H ) ] (2) was generated under similar reaction conditions with [Re (CO) ]. Similarly, when [Mn (CO) ] was treated with Na[(H B)abz], bis(σ)borate complex [Mn(CO) (μ-H) BH(HN CSC H )] (3) and the agostic complex [Mn(CO) (μ-H)BH(HN CSC H ) ] (4) were formed. To probe the potential formation of agostic complexes of the heavier group 7 metals, we carried out the photolysis of [M (CO) ] with Na[(H B)mp ] and found that [M(CO) (μ-H)BH(C H NS) ] (5: M=Re; 6: M=Mn) was formed in moderate yield. Complexes 1 and 3 feature a (κ -H,H,N) coordination mode, whereas 4, 5, and 6 display both (κ -H,N,N) and (κ -H,S,S) modes of the corresponding ligands. To investigate the lability of the CO ligands of 1 and 3, we treated the complexes with phosphine ligands that generated novel bis(σ)borate complexes [Mn(μ-H) (BHNCSC H )(NR)(CO) PL L'] (R=NCSC H ; 7 a: L=L'=Ph; 7 b: L=Ph, L'=Me) and [Mn(μ-H) BHN(NCSC H )R(CO) PL L'] (R=NCSC H ; 8 a: L=L'=Ph; 8 b: L=Ph, L'=Me). Complexes 7 and 8 are structural isomers with different coordination modes of the bbza ligand. In addition, DFT calculations were performed to shed some light on the bonding and electronic structures of these complexes.

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“…[18] In the course of our recent studies for the isolation of diverse borate complexes and E-H bond activations (E = C, B or Si), [20] 3) with different types of borate ligands that showed diverse reactivity patterns and produced unusual σ-borate complexes. [21,22] As a result, the scope for the isolation of different borate complexes by tuning the electronic and steric properties of the metal, ancillary ligand(s) and the heterocycles associated with borate ligand became of interest.…”

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Coordination and Hydroboration of Ru(II)‐Borate Complexes: Dihydridoborate vs. Bis(dihydridoborate)

Pathak

Gayen

Saha

et al. 2022

Chemistry A European J

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Treatment of [Cp*RuCl2]2, 1, [(COD)IrCl]2, 2 or [(p‐cymene)RuCl2]2, 3 (Cp*=η5‐C5Me5, COD= 1,5‐cyclooctadiene and p‐cymene=η6‐iPrC6H4Me) with heterocyclic borate ligands [Na[(H3B)L], L1 and L2 (L1: L=amt, L2: L=mp; amt=2‐amino‐5‐mercapto‐1,3,4‐thiadiazole, mp=2‐mercaptopyridine) led to the formation of borate complexes having uncommon coordination. For example, complexes 1 and 2 on reaction with L1 and L2 afforded dihydridoborate species [LAM(μ‐H)2BHL] 4–6 (4: LA=Cp*, M=Ru, L=amt; 5: LA=Cp*, M=Ru, L=mp; 6: LA=COD, M=Ir, L=mp). On the other hand, treatment of 3 with L2 yielded cis‐ and trans‐bis(dihydridoborate) species, [Ru{(μ‐H)2BH(mp)}2], cis‐7 and trans‐7. The isolation and structural characterization of fac‐ and mer‐[Ru{(μ‐H)2BH(mp)}{(μ‐H)BH(mp)2}], 8 from the same reaction offered an insight into the behaviour of these dihydridoborate species in solution. Fascinatingly, despite having reduced natural charges on Ru centres both at cis‐and trans‐7, they underwent hydroboration reaction with alkynes that yielded both Markovnikov and anti‐Markovnikov addition products, 10 a–d.

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Reactivity of Diruthenium and Dirhodium Analogues of Pentaborane(9): Agostic versus Boratrane Complexes

Cited by 27 publications

References 48 publications

Activation of C–H and B–H bonds through agostic bonding: an ELF/QTAIM insight

Activation of C–H and B–H bonds through agostic bonding: an ELF/QTAIM insight

Design, Synthesis, and Chemistry of Bis(σ)borate and Agostic Complexes of Group 7 Metals

Coordination and Hydroboration of Ru(II)‐Borate Complexes: Dihydridoborate vs. Bis(dihydridoborate)

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