Heavier Group 13 Metal(I) Heterocycles Stabilized by Sterically Demanding Diiminophosphinates: A Structurally Characterized Monomer–Dimer Pair For Gallium

Hawley, Andrew L.; Ohlin, C. André; Fohlmeister, Lea; Stasch, Andreas

doi:10.1002/chem.201604495

Cited by 29 publications

(21 citation statements)

References 89 publications

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“…However, both compounds II and IIIa exhibit metal–metal bonds in the solid state, which benefit significantly from dispersion stabilization, as revealed by computational studies. London dispersion forces contribute critically to the thermodynamic stabilities of seemingly reactive main group element compounds and also make large contributions to the dimerization enthalpies of group 13 diyls …”

Section: Introductionsupporting

confidence: 57%

“…The last decades have seen rapid development of the chemistry of low oxidation state group 13 species, and numerous compounds have been synthesized since the seminal work on group 13 diyls in the last century . Although the first example of a stable group 13 element analogue of carbenes was not isolated until 1999, today examples are known for aluminium, gallium, indium,, and thallium,, and they have found numerous applications as ligands in transition metal complexes, for the stabilization of unusual molecules, and as reagents for the activation of small molecules and strong bonds . The corresponding neutral boron compound, that is, a borylene stabilized by one Lewis base, remains undiscovered to date .…”

Section: Introductionmentioning

confidence: 99%

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En Route to Bis‐Carbene Analogues of the Heavier Group 13 Elements: Consideration of Bridging Group and Metal(I) Source

Desat

Kretschmer

2018

Chemistry A European J

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With the aim of exploring the effect of steric constraints imposed on the metal-metal interaction of bis-carbene analogues of thallium by the linking scaffold, seven dinuclear thallium diyls with a series of rigid, semirigid, and flexible bridging scaffolds were synthesized. The solid-state molecular structures were determined for four of these compounds by single-crystal XRD and compared with the results of DFT calculations, which were performed for all substances. These compounds serve as models to investigate the metal-metal distance in the absence of co-coordinated molecules (additional ligands, solvent molecules). In addition, the effect of the metal(I) precursor, and more specifically the counterion, on the synthetic access to bis-carbene analogues of indium and thallium was investigated. For indium, only InI yields the desired dinuclear indium diyl. With InBr no reaction was observed, and using InCl gave rise to a mononuclear indium(III) compound. For thallium, both TlI and TlBr allow access to the related bis-carbene analogue, although the yield with the latter is significantly lower. In contrast, no reactions were observed with TlCl and TlBF .

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Section: Introductionsupporting

confidence: 57%

Section: Introductionmentioning

confidence: 99%

En Route to Bis‐Carbene Analogues of the Heavier Group 13 Elements: Consideration of Bridging Group and Metal(I) Source

Desat

Kretschmer

2018

Chemistry A European J

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“…Figure shows the known heavier group 13 metal complexes with iminophosphonamide ligands. The Ga(I), In(I) and Tl(I) complexes have very recently been reported by Stasch (see Figure ). These low valent metal(I) heterocycles are notable and demonstrate the ability of iminophosphonamides to stabilize low valent state of heavier group 13 elements.…”

Section: Introductionsupporting

confidence: 52%

“…These low valent metal(I) heterocycles are notable and demonstrate the ability of iminophosphonamides to stabilize low valent state of heavier group 13 elements. However, to the best of our knowledge, no complex of In(III) with iminophosphamide, has been reported till date and the only known In(I) complex has been that of Stasch, [Ph 2 P(N‐2,6‐iPr 2 C 6 H 3 ) 2 ]In …”

Section: Introductionmentioning

confidence: 99%

Heteroleptic Iminophosphonamide In(III) Complexes: Source of Mild Lewis Acid Indium Centers

2017

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New In(III) complexes with iminophosphonamide ligand are reported for the first time. Reaction of the lithium iminophosphonamide, LLi⋅2OEt2 with InCl3 afforded the heterobimetallic compound, LInCl(μ‐Cl)2Li⋅2OEt2 (1) (L=(2,6‐iPr2C6H3N)P(Ph2)(NtBu)). To prevent the formation of LiCl adduct in 1, and to obtain the targeted LInCl2 molecule, potassium salt of the ligand LK was reacted with InCl3 that gave the adduct LInCl2(THF) (2). Formation of compounds 1 and 2 can be considered an outcome of the In(III) centers to exhibit Lewis acidity. Reaction of LK with InCl3 in non coordinating solvent toluene gave the dimer [LInCl(μ‐Cl)]2 (3) and its further treatment with Ph2P(=O)NHtBu afforded the adduct, LInCl2⋅(O=P(Ph2)NHtBu) (4). Formation of the dimer 3 or the adduct 4 are again the reminiscent of the Lewis acid tendency of In(III) centers. Complexes 1–4 have been characterized using multinuclear NMR and HRMS. The single crystal X‐ray structures of 1, 3 and 4 have also been elucidated.

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“…Later on, the use of sterically demanding ligands 2,6‐Trip 2 C 6 H 3 (Trip = 2,4,6‐ i Pr 3 C 6 H 2 ) or 2,6‐Diip 2 C 6 H 3 (Diip = 2,6‐ i Pr 2 C 6 H 3 ) provided stable monomers [(2,6‐Trip 2 C 6 H 3 )M] (M = In, Tl) or weakly bonded dimers [(2,6‐Diip 2 C 6 H 3 )M] 2 (M = Ga, In) . The field of subvalent monomeric complexes of group 13 elements was extended by the utilization of the electron‐rich ligands such as tri(3,5‐di‐ tert ‐butylpyrazolyl)hydroborate, β‐diketiminates, guanidinates, or diiminophosphinates …”

Section: Introductionmentioning

confidence: 99%

Synthesis of N→Ga Coordinated Gallium(II)–Gallium(II) Compounds

et al. 2018

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Synthesis of the N→Ga coordinated gallium(II)gallium(II) compounds containing the N,C,N-chelating ligand L [L: {2,6-(Me 2 NCH 2 ) 2 C 6 H 3 } -] is reported. Attempts to stabilize the subvalent digallene [LGa] 2 by reduction of [L(Cl)Ga] 2 (1) or by Recent studies also showed that the stabilization of 14 and 15 main group elements in oxidation state +I can be accompanied by the utilization of Y,C,Y-chelating ligands. [8] To the best of our knowledge, the field of subvalent derivatives of group 13 metals containing the pincer type ligand is practically unexplored. In 1994 A. H. Cowley reported the stabilization of LM{Co(CO) 4 } 2 [M = Ga, In, L is {2,6-(Me 2 NCH 2 ) 2 C 6 H 3 } -] by the substitution reaction of LMCl 2 with NaCo(CO) 4 . [9] In 1998, the same group synthesized indium(II)-indium(II) compound [L(Cl)In] 2 by the reduction of LInCl 2 with the dilithium salt of diisopropylaminoborole. [10] These facts lead us to extend the current knowledge of subvalent derivatives of group 13 metals stabilized by N,C,N-chelating ligand L.[a] 1620 hydrogen elimination from [L(H)Ga] 2 (2) failed, but an unexpected complex, [L(C 6 H 5 CH 2 )Ga] 2 (3), was isolated. It is possibly the product of the reaction of the parent digallene [LGa] 2 with toluene. Results and DiscussionComplex LGaCl 2 was prepared according to the literature procedure, [11] and its reaction with KC 8 provided gallium(II)-gallium(II) compound [L(Cl)Ga] 2 (1; Scheme 1). Scheme 1. Synthesis of compound [L(Cl)Ga] 2 (1).

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Heavier Group 13 Metal(I) Heterocycles Stabilized by Sterically Demanding Diiminophosphinates: A Structurally Characterized Monomer–Dimer Pair For Gallium

Cited by 29 publications

References 89 publications

En Route to Bis‐Carbene Analogues of the Heavier Group 13 Elements: Consideration of Bridging Group and Metal(I) Source

En Route to Bis‐Carbene Analogues of the Heavier Group 13 Elements: Consideration of Bridging Group and Metal(I) Source

Heteroleptic Iminophosphonamide In(III) Complexes: Source of Mild Lewis Acid Indium Centers

Synthesis of N→Ga Coordinated Gallium(II)–Gallium(II) Compounds

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