Mercapto-benzothiazolyl based ruthenium(<scp>ii</scp>) borate complexes: synthesis and reactivity towards various phosphines

Zafar, Mohammad; Ramalakshmi, Rongala; Pradhan, Alaka Nanda; Pathak, Kriti; Roisnel, Thierry; Halet, Jean‐François; Ghosh, Sundargopal

doi:10.1039/c9dt00498j

Cited by 11 publications

(12 citation statements)

References 84 publications

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“…Accordingly, the C10−C11 and C10−O1 bond distances of 1.547(5) Å and 1.391(4) Å, respectively correspond to single bonds. The short P1−O2 bond distance (1.516(3) Å) supports P=O double bond character [17d,18b,d,f] and the Rh1−P1 bond distance (2.216(1) Å) is rather short. A strong hydrogen bond (C)−OH⋅⋅⋅O(=P) (O1−O2 distance of 2.595(4) Å; O1−H1A−O2 angle of 134.3°) [22] is observed between the hydroxyalkyl and the phosphoryl ligand.…”

Section: Resultsmentioning

confidence: 75%

Experimental and DFT studies on Hexacoordinated acyl(alkyl)and Pentacooordinated Hydroxyalkyl(phosphinite)erhodium(III). Catalytic Hydrolysis of Ammonia Borane

et al. 2021

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[Rh(nbd)Cl]2 (nbd=norbornadiene) reacts with quinoline‐8‐carbaldehyde (C9H6NCHO) and pyrazole (Hpz) affording, depending on Rh/Hpz ratio, acyl‐alkyl [Rh(μ‐Cl)(C9H6NCO)(Hpz)(σ‐C7H9)]2 (1) or [RhCl(C9H6NCO)(Hpz)2(σ‐norbornenyl)] (2), stereoselectively as confirmed by DFT calculations. Hydrogen bond between NH‐pyrazole and O‐acyl occurs. 1 and 2 react with diphenylphosphine oxide (SPO) giving 16e [RhCl(C9H6NC(nbyl))(Ph2PO)(Hpz)] (3) through SPO κ1‐P‐coordination, C−C bond coupling between acyl and norbornenyl and outer‐sphere O(P)‐to‐O(C) hydrogen transfer. 3 shows distorted trigonal bipyramidal structure with weak intramolecular (C)−OH⋅⋅⋅O(=P) and NH⋅⋅⋅Cl hydrogen bonds. DFT calculations indicate this 16e structure being favoured by σ‐ and π‐type orbital multi‐overlapping between pyrazole and both the OH⋅⋅⋅O and chlorine and by intermolecular forces in the crystal. Solutions of 3 contain an equilibrium between trigonal bipyramid and a square‐planar pyramid with OH interacting with phosphoryl and NH, confirmed by DFT 13C NMR calculations. 1 is very efficient homogeneous catalyst for H3N−BH3 hydrolysis to release hydrogen under air.

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Section: Resultsmentioning

confidence: 75%

Experimental and DFT studies on Hexacoordinated acyl(alkyl)and Pentacooordinated Hydroxyalkyl(phosphinite)erhodium(III). Catalytic Hydrolysis of Ammonia Borane

et al. 2021

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“…Similarly, as shown in Scheme , treatment of 1 a – d with [H 2 B(mbz) 2 ] − led to the formation of N,S‐chelating Ru species, [(κ 2 ‐N,S‐L)PR 3 Ru{κ 3 ‐H,S,S ’ −H 2 B(L) 2 }], ( 2 a’ : R=Ph, 2 b’ : R=Cy, 2 c’ : R=OMe, 2 d’ : R=OPh; L=C 7 H 4 NS 2 ). The chelating complexes were isolated as crystalline solids and were characterized by 1 H, 11 B{ 1 H}, 13 C{ 1 H}, 31 P{ 1 H} NMR as well as IR spectroscopy and in some cases by X‐ray crystallographic analyses.…”

Section: Resultsmentioning

confidence: 99%

“…The bidentate N,S‐donor group forms a four‐membered chelate ring with a bite angle of 67.08(13)°, comparable to that of [(PPh 3 ) 2 )Ru( N , S ‐mbz) 2 )] (67.295(11)°) . The Ru1‐S6‐C21‐N3 ring is almost flat with a torsion angle of −0.7(5)°, larger than that of 2 d’ (−3.5(4)°) . The Ru1−S6 distance of 2.4741(18) Å in 2 a’ is significantly longer than the Ru1−S2 and Ru1−S4 distances in 2 a’ (2.3268(18) and 2.3469(16) Å respectively) and other ruthenium complexes .…”

Section: Resultsmentioning

confidence: 99%

Five‐Membered Ruthenacycles: Ligand‐Assisted Alkyne Insertion into 1,3‐N,S‐Chelated Ruthenium Borate Species

Zafar

Ramalakshmi

Pathak

et al. 2019

Chemistry A European J

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“…In order to determine the role of ancillary ligands in the stability of the TM σ-borate complexes, the reaction of [( p -cymene)RuCl 2 (PR 3 )] with Na[H 2 B(C 7 H 4 NS 2 ) 2 ] ( p -cymene = η 6 -( p - i PrC 6 H 4 Me)) was performed, yielding the ruthenium σ-borate complexes [(κ N ,κ S -C 7 H 4 NS 2 )(R 3 P)RuH 2 B(L) 2 }] (R = Ph ( 33a ), OPh ( 33b )) and the bis(σ-borate) complex [Ru(H 2 B(C 7 H 4 NS 2 ) 2 ) 2 ] ( 34 ) (Scheme ). , The presence of upfield 1 H NMR chemical shifts at ca. −15 ppm suggested the presence of a Ru– H –B unit.…”

Section: Tetracoordinate σ-Borane/borate Complexesmentioning

confidence: 99%

Recent Advances in the Synthesis and Reactivity of Transition Metal σ-Borane/Borate Complexes

et al. 2021

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Conspectus The coordination of an element–element σ bond to a transition metal (TM) is both a fundamentally intriguing binding mode and of critical importance to metal-mediated bond activation mechanisms and catalysis, particularly the hotly contested field of C–H activation. TM σ complexes of dihydrogen (i.e., H–H) and silanes (H–SiR3) have been extensively studied, the latter being of interest as models for the (generally unstable and unisolable) σ complexes of alkanes (i.e., H–CR3). TM σ complexes of hydroboranes and hydroborates (i.e., H–BR2, H–BR3, (H−)2BR2) are somewhat less well studied but similarly have relevance to catalytic borylation reactions that are of high current interest to organic synthesis. Our two research groups have made significant contributions to elaborating the family of σ-borane/-borate complexes using two distinct approaches: while the Ghosh group generally starts from hydrogen-rich tetracoordinate boron species such as borates, the Braunschweig group starts from hypovalent and/or hypocoordinate boron building blocks. Through these two approaches, a wide range of species containing one or two σ-bound B–H ligands have been prepared, some with additional chelating donor sites. Over the past 2 years, the body of work on σ-borane/-borate complexes from our two research groups has significantly expanded, with a combined nine published articles in 2019–2020 alone. Very recent work from the Braunschweig group has led to the synthesis of the first bis(σ)-borane complexes of group 6 metals, as well as the synthesis of a series of novel bis(σ)-borane and bis(σ)-borate complexes of ruthenium and iridium, the former being useful precursors for pentacoordinate borylene complexes of Ru. Recent work from the Ghosh group has uncovered a remarkable diversity of structures with σ(B–H)-bound ligands from the combination of borohydrides and nitrogen/chalcogen-containing groups and heterocycles. These reactions, while in some cases producing conventional scorpionate-type chelating products, more frequently undergo fascinating rearrangements with unpredictable outcomes. This Account aims to highlight this recent acceleration of research progress in this area, particularly the distinct but related approaches ofand complexes produced byour two research groups, in addition to relevant works from other groups where appropriate.

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Mercapto-benzothiazolyl based ruthenium(ii) borate complexes: synthesis and reactivity towards various phosphines

Abstract: Ruthenium complexes featuring phosphinate and dual Ru⋯H–B interactions between Ru and B–H bonds of borate ligands supported by mercapto-benzothiazolyl heterocycles have been synthesized.

Cited by 11 publications

References 84 publications

Experimental and DFT studies on Hexacoordinated acyl(alkyl)and Pentacooordinated Hydroxyalkyl(phosphinite)erhodium(III). Catalytic Hydrolysis of Ammonia Borane

Experimental and DFT studies on Hexacoordinated acyl(alkyl)and Pentacooordinated Hydroxyalkyl(phosphinite)erhodium(III). Catalytic Hydrolysis of Ammonia Borane

Five‐Membered Ruthenacycles: Ligand‐Assisted Alkyne Insertion into 1,3‐N,S‐Chelated Ruthenium Borate Species

Recent Advances in the Synthesis and Reactivity of Transition Metal σ-Borane/Borate Complexes

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