The Organometallic Chemistry of Group 9 Poly(pyrazolyl)borate Complexes

Crossley, Ian R.

doi:10.1016/s0065-3055(07)56004-1

Cited by 26 publications

(15 citation statements)

References 235 publications

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“…A recent review details the wide ranging chemistry of rhodium hydrotris(pyrazolyl)borates, 5 including examples of C-H activation and of polymerisation catalysis. Studies 6 of the redox chemistry of rhodium(I) Tp¢ complexes resulted in the isolation of rhodium(II) species stabilised through coordination of the third pyrazolyl ring to rhodium.…”

Section: Introductionmentioning

confidence: 99%

A novel route to rhodaboratranes [Rh(CO)(PR3){B(taz)3}]+via the redox activation of scorpionate complexes [RhLL′Tt]

et al. 2009

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The reaction of a mixture of the sodium salts of dihydrobis(4-ethyl-3-methyl-5-thioxo-1,2,4-triazolyl)borate, NaBt, and hydrotris(4-ethyl-3-methyl-5-thioxo-1,2,4-triazolyl)borate, NaTt, with [{Rh(cod)(mu-Cl)}2] gave [Rh(cod)Bt] and [Rh(cod)Tt], which separately react with CO gas to give the unstable dicarbonyl [Rh(CO)2Bt] and an equilibrium mixture of two isomers of [Rh(CO)2Tt] and [(RhTt)2(mu-CO)3], respectively. Tertiary phosphorus donor ligands react with the mixture of [Rh(CO)2Tt] and [(RhTt)2(mu-CO)3] to give [Rh(CO)(PR3)Tt] (R = Cy, NMe(2), Ph or OPh) and [Rh{P(OPh)3}2Tt] in which rhodium is bound to two sulfur atoms of the scorpionate ligand; the B-H bond is directed towards the metal to give an agostic-like B-H...Rh interaction. Dinuclear [(RhTt)2(mu-CO)3] has kappa3[S3]-bound Tt ligands with a rhodium-rhodium bond bridged by three carbonyls. In solution the mononuclear Tt complexes undergo rapid dynamic interchange of the three thioxotriazolyl rings, probably via kappa3[S3]-coordinated intermediates. The monocarbonyls [Rh(CO)(PR3)Tt] (R = Cy, NMe2 or Ph) react with two equivalents of [Fe(eta-C5H5)2][PF6] in the presence of triethylamine to give the monocationic rhodaboratranes [Rh(CO)(PR3){B(taz)3}]+, with boron NMR spectroscopy providing evidence for the boron-rhodium bond. In the solid state, rhodium is bound to the three sulfur atoms and the boron of the B(taz)3 fragment, forming a tricyclo[3.3.3.0] cage. The phosphine is trans to the Rh-B bond, the long Rh-P bond indicating a pronounced trans influence for the coordinated boron. The cation [Rh(CO)(PPh3){B(taz)3}]+ reacts with [NBu(n)(4)]I to give [Rh(PPh3)I{B(taz)3}], in which the halide is trans to the Rh-B bond, and a second species, possibly [Rh(CO)I{B(taz)3}]. The dirhodaboratrane [Rh2(PCy3){B(taz)3}2][PF6]2, a minor byproduct in the synthesis of [Rh(CO)(PCy3){B(taz)3}][PF6], has a distorted square pyramidal rhodium atom with a vacant site trans to the Rh-B bond. The second metal has four coordination sites filled by the sulfur and boron atoms of a second B(taz)3 unit, the remaining octahedral sites occupied by two of the sulfur atoms of the first B(taz)3 unit which therefore bridges the two rhodium atoms.

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Section: Introductionmentioning

confidence: 99%

A novel route to rhodaboratranes [Rh(CO)(PR3){B(taz)3}]+via the redox activation of scorpionate complexes [RhLL′Tt]

et al. 2009

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“…All chemicals and reagents were of reagent grade quality and were used as received without further purification. The potassium salt of the scorpionate ligand K[Ph 2 Bp] was synthesized as previously reported . Dichloromethane was freshly distilled from CaH 2 .…”

Section: Methodsmentioning

confidence: 99%

“…These complexes undergo a rich variety of chemistry through chloro bridge cleavage reactions, leading to the formation of interesting neutral and cationic mononuclear complexes . In addition, rhodium(III) and iridium(III) complexes containing scorpionate ligands have recently attracted considerable attention because of their ability to activate the aliphatic and aromatic C–H bonds of hydrocarbons and other substrates …”

Section: Introductionmentioning

confidence: 99%

Boron Functionalization and Unusual B–C Bond Activation in Rhodium(III) and Iridium(III) Complexes with Diphenylbis(pyrazolylborate) Ligands (Ph₂Bp)

Pettinari¹,

Pettinari²,

Marchetti³

et al. 2013

Organometallics

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The Rh(III) and Ir(III) pentamethylcyclopentadienyl compounds [M(Cp*)(κ2-Ph2Bp)Cl] (M = Rh, 1; M = Ir, 4) were readily prepared from interaction of the salt K[Ph2Bp] (Ph2Bp = diphenylbis(pyrazolyl)borate) and the [M(Cp*)Cl2]2 dimer precursors in dichloromethane under anhydrous conditions. When the same reactions were carried out in non-anhydrous conditions by using acetonitrile as solvent, we observed, in the case of Rh, both B–N bond hydrolysis and Rh–C(Ph) bond activation with the formation of the hydroxy(pyrazolyl)borate complex [Rh(Cp*)(Ph){κ2-(pz)(OH)BPh2}] (2). In contrast, in the case of Ir only B–N hydrolysis was observed and the ionic species [Ir(Cp*)(Hpz){κ2-(pz)(OH)BPh2}]Cl (5) was obtained, upon coordination of the liberated Hpz. Additionally, by reaction of 1 with AgClO4 in acetonitrile, the ionic [Rh(Cp*)(Ph){κ2-(pz)(OH)B(OH)}]ClO4 (3) was isolated. Complexes 1–3 and 5 have been structurally characterized by X-ray crystallography. Spectral studies have been performed for all species, together with a computational DFT modeling investigation. A decomposition mechanism for the diphenylbis(pyrazolyl)borate ligand in the different complexes is proposed.

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“…Rapenne et al [63] described the synthesis of various pentaphenylcyclopentadienyl hydrotris(pyrazolyl)borate ligands and the peculiar reactivity of such hindered ligands in their coordination to a ruthenium(II) center. More recently the volume 56 of the Advances in Organometallic Chemistry has been devoted to "The Organotransition Metal Chemistry of Poly(pyrazolyl)borates" [64][65][66][67].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Properties of Poly(pyrazolyl)borate and Related Boron-Centered Scorpionate Ligands. Part A: Pyrazole-Based Systems

Santini¹,

Pellei²,

Lobbia³

et al. 2010

MROC

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This review is intended to cover the developments in the chemistry of poly(azolyl)borates through the years 2000-2008, based on the main synthetic methods, coordination properties, spectroscopic and structural features of this important class of ligands. The subject matter is the chemistry of substituted bis-, tris-and tetrakis-(pyrazolyl)borate ligands. In this review we provide essential information to allow the reader to probe more deeply into the main aspects of the chemistry of these fascinating and flexible ligands. This review would also demonstrate the enormous potential of poly(pyrazolyl)borates chemistry, as also the future perspectives in this field.

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The Organometallic Chemistry of Group 9 Poly(pyrazolyl)borate Complexes

Cited by 26 publications

References 235 publications

A novel route to rhodaboratranes [Rh(CO)(PR3){B(taz)3}]+via the redox activation of scorpionate complexes [RhLL′Tt]

A novel route to rhodaboratranes [Rh(CO)(PR3){B(taz)3}]+via the redox activation of scorpionate complexes [RhLL′Tt]

Boron Functionalization and Unusual B–C Bond Activation in Rhodium(III) and Iridium(III) Complexes with Diphenylbis(pyrazolylborate) Ligands (Ph₂Bp)

Synthesis and Properties of Poly(pyrazolyl)borate and Related Boron-Centered Scorpionate Ligands. Part A: Pyrazole-Based Systems

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The Organometallic Chemistry of Group 9 Poly(pyrazolyl)borate Complexes

Cited by 26 publications

References 235 publications

A novel route to rhodaboratranes [Rh(CO)(PR3){B(taz)3}]+via the redox activation of scorpionate complexes [RhLL′Tt]

A novel route to rhodaboratranes [Rh(CO)(PR3){B(taz)3}]+via the redox activation of scorpionate complexes [RhLL′Tt]

Boron Functionalization and Unusual B–C Bond Activation in Rhodium(III) and Iridium(III) Complexes with Diphenylbis(pyrazolylborate) Ligands (Ph2Bp)

Synthesis and Properties of Poly(pyrazolyl)borate and Related Boron-Centered Scorpionate Ligands. Part A: Pyrazole-Based Systems

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Boron Functionalization and Unusual B–C Bond Activation in Rhodium(III) and Iridium(III) Complexes with Diphenylbis(pyrazolylborate) Ligands (Ph₂Bp)