Synthesis and characterization of three nickel(ii) carborane complexes containing nido- or closo-carborane diphosphine ligand

Dou, Jianmin; Zhang, Daopeng; Li, Dacheng; Wang, Daqi

doi:10.1016/j.jorganchem.2006.09.018

Cited by 18 publications

(6 citation statements)

References 37 publications

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“…The loss of ligand chalcogen was very rapid with [ Table 5) confirmed the spectroscopic data. The structural parameters of 19 are similar to those of [ [31] (the Ni À Cl distances are 0.03 shorter than the Ni À Br distances).…”

Section: Reactivity Of Monochalcogenide Diphosphinessupporting

confidence: 52%

“…This is evidenced in the 31 P NMR spectra and in the chemical properties. The electron-acceptor character of the carboranyl cluster lowers the charge density on the phosphorus atom, and this results in 1) deshielded P resonances in the 31 P NMR spectrum; 2) increased stability of carboranyl diphosphines against oxidation in the solid state and in solution, even under air; and 3) polarisation of the P=E bond towards phosphorus, which weakens this bond.…”

Section: Discussionmentioning

confidence: 81%

“…Characterization of oxidized closo carboranyl phosphines: Spectroscopic characterization: Carboranyl phosphine oxidation products were characterized by IR and 1 H, 13 C{ 1 H}, 31 P{ 1 H} and 11 B NMR spectroscopy. Strong broad absorptions at 2644-2550 cm À1 , due to B À H stretching, dominate the IR spectra and support a closo cluster structure.…”

Section: Resultsmentioning

confidence: 99%

“…The mixture was kept at room temperature for between one and five days, depending on the metal. The reactions were monitored by 31 P NMR and 11 B NMR spectroscopy, and the data were compared with literature values. Single crystals suitable for X ray diffraction were grown by slow evaporation from dichloromethane/diethyl ether solution.…”

Section: Ja C H T U N G T R E N N U N G (Hh) =mentioning

confidence: 99%

“…Lines join equivalent positions in the three compounds.Se bond and the non-symmetric nature of the oxidized species. For instance, the31 P{ 1 H} NMR spectrum of 1-SePPh 2 -2-PPh 2 -1,2-closo-C 2 B 10 H 10 (15) showed two doublets, at d = 46.48 and 10.48 ppm, with a coupling constant of 3 J-A C H T U N G T R E N N U N G ( 31 P, 31 P) = 27 Hz. The resonance at d = 46.48 ppm suggests formation of a P=Se bond, whereas the signal at d = 10.48 ppm corresponds to unoxidized phosphorus.…”

mentioning

confidence: 99%

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Uncommon Coordination Behaviour of P(S) and P(Se) Units when Bonded to Carboranyl Clusters: Experimental and Computational Studies on the Oxidation of Carboranyl Phosphine Ligands

Popescu

Laromaine

Teixidor

et al. 2011

Chemistry A European J

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Oxidation of closo-carboranyl diphosphines 1,2-(PR(2))(2)-1,2-closo-C(2)B(10)H(10) (R=Ph, iPr) and closo-carboranyl monophosphines 1-PR(2)-2-R'-1,2-closo-C(2)B(10)H(10) (R=Ph, iPr, Cy; R'=Me, Ph) with hydrogen peroxide, sulfur and elemental black selenium evidences the unique capacity of the closo-carborane cluster to produce uncommon or unprecedented P/P(E) (E=S, Se) and P=O/P=S chelating ligands. When H(2)O(2) reacts with 1,2-(PR(2))(2)-1,2-closo-C(2)B(10)H(10) (R=Ph, iPr), they are oxidized to 1,2-(OPR(2))(2)-1,2-closo-C(2)B(10)H(10) (R=Ph, iPr). However, when S and Se are used, different reactivity is found for 1,2-(PPh(2))(2)-1,2-closo-C(2)B(10)H(10) and 1,2-(PiPr(2))(2)-1,2-closo-C(2)B(10)H(10). The reaction with sulfur produces mono- and dioxidation products for R=Ph, whereas Se produces the mono-oxidation product only. For R=iPr, only monooxidation takes place with S, and the second C(c)-PiPr(2) bond breaks to yield 1-SPiPr(2)-1,2-closo-C(2)B(10)H(11). When Se is used, only 1-SePiPr(2)-1,2-closo-C(2)B(10)H(11) is formed. The potential of the mono-chalcogenide carboranyl diphosphines 1-EPPh(2)-2-PPh(2)-1,2-closo-C(2)B(10)H(10) (E=S, 9; Se, 15) to behave as unsymmetric chelating bidentate ligands was studied for different metal complexes, different solvents and in the solid state. Dechalcogenation takes place in each case. Computational studies provided information on the P=E (E=S, Se) bonds. Steric effects block the bonding ability of the P=E group due to interactions between the chalcogen and the neighbouring hydrogen atoms (three from the phenyl rings and one from the carborane cluster). The electronic effects originate from the strongly electron-withdrawing character of the closo carborane cluster, which polarizes the P=E (E=S, Se) bond towards the phosphorus atom. As a consequence, the E atom is the electron-poor site and the P atom the electron-rich site in the P=E bond.

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Section: Reactivity Of Monochalcogenide Diphosphinessupporting

confidence: 52%

Section: Discussionmentioning

confidence: 81%

Section: Resultsmentioning

confidence: 99%

Section: Ja C H T U N G T R E N N U N G (Hh) =mentioning

confidence: 99%

mentioning

confidence: 99%

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Uncommon Coordination Behaviour of P(S) and P(Se) Units when Bonded to Carboranyl Clusters: Experimental and Computational Studies on the Oxidation of Carboranyl Phosphine Ligands

Popescu

Laromaine

Teixidor

et al. 2011

Chemistry A European J

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A Bis(silylene)‐Substituted ortho‐Carborane as a Superior Ligand in the Nickel‐Catalyzed Amination of Arenes

et al. 2016

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The synthesis and structure of the first 1,2-bis-(NHSi)-substituted ortho-carborane [(LSi:)C] 2 B 10 H 10 (termed SiCCSi)i sr eported (NHSi = N-heterocyclic silylene;L = PhC(NtBu) 2 ). Its suitability to serve as ar eliable bis(silylene) chelating ligand for transition metals is demonstrated by the formation of [SiCCSi]NiBr 2 and [SiCCSi]Ni(CO) 2 complexes. The CO stretching vibration modes of the latter indicate that the Si II atoms in the SiCCSi ligand are even stronger s donors than the P III atoms in phosphines and C II atoms in Nheterocyclic carbene (NHC) ligands.M oreover,t he strong donor character of the [SiCCSi]ligand enables [SiCCSi]NiBr 2 to act as an outstanding precatalyst (0.5 mol %loading) in the catalytic aminations of arenes,s urpassing the activity of previously knownm olecular Ni-based precatalysts (1-10 mol %). Scheme 1. Multidentate NHSi ligands.

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A Bis(silylene)‐Substituted ortho‐Carborane as a Superior Ligand in the Nickel‐Catalyzed Amination of Arenes

et al. 2016

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The synthesis and structure of the first 1,2-bis(NHSi)-substituted ortho-carborane [(LSi:)C]2 B10 H10 (termed SiCCSi) is reported (NHSi=N-heterocyclic silylene; L=PhC(NtBu)2 ). Its suitability to serve as a reliable bis(silylene) chelating ligand for transition metals is demonstrated by the formation of [SiCCSi]NiBr2 and [SiCCSi]Ni(CO)2 complexes. The CO stretching vibration modes of the latter indicate that the Si(II) atoms in the SiCCSi ligand are even stronger σ donors than the P(III) atoms in phosphines and C(II) atoms in N-heterocyclic carbene (NHC) ligands. Moreover, the strong donor character of the [SiCCSi] ligand enables [SiCCSi]NiBr2 to act as an outstanding precatalyst (0.5 mol % loading) in the catalytic aminations of arenes, surpassing the activity of previously known molecular Ni-based precatalysts (1-10 mol %).

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Synthesis and characterization of three nickel(ii) carborane complexes containing nido- or closo-carborane diphosphine ligand

Cited by 18 publications

References 37 publications

Uncommon Coordination Behaviour of P(S) and P(Se) Units when Bonded to Carboranyl Clusters: Experimental and Computational Studies on the Oxidation of Carboranyl Phosphine Ligands

Uncommon Coordination Behaviour of P(S) and P(Se) Units when Bonded to Carboranyl Clusters: Experimental and Computational Studies on the Oxidation of Carboranyl Phosphine Ligands

A Bis(silylene)‐Substituted ortho‐Carborane as a Superior Ligand in the Nickel‐Catalyzed Amination of Arenes

A Bis(silylene)‐Substituted ortho‐Carborane as a Superior Ligand in the Nickel‐Catalyzed Amination of Arenes

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