Gallane adducts of bifunctional Group V ligands; crystal structures of (GaH3)2(tmen) and (GaH3)2(dmpe)

O’Hare, Dermot; Foord, John S.; Page, Timothy C. M.; Whitaker, T. J.

doi:10.1039/c39910001445

Cited by 38 publications

(11 citation statements)

References 7 publications

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“…The gallium−chloride distance of 2.2525(9) Å compares well with that found in Ga(Pc)Cl (2.179(6) Å) . The gallium−phosphorus bond lengths of 2.4930(8) Å and 2.4695(8) Å are well within the normal range associated with such bonds (∼2.4−2.7 Å). − The gallium−nitrogen distances of 1.968(2) and 1.966(2) Å are normal in terms of gallium−amide bonds …”

Section: Resultssupporting

confidence: 64%

Pyramidal Inversion at Phosphorus Facilitated by the Presence of Proximate Lewis Acids. Coordination Chemistry of Group 13 Elements with the Macrocyclic Bis(amidophosphine) Ligand [P₂N₂] ([P₂N₂] = [PhP(CH₂SiMe₂NSiMe₂CH₂)₂PPh])

1998

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Investigations on the preparation of four- and five-coordinate aluminum and gallium bis(amidophosphine) derivatives are reported. The reaction of the macrocyclic ligand precursor anti-Li(2)(THF)(2)[P(2)N(2)] ([P(2)N(2)] = [PhP(CH(2)SiMe(2)NSiMe(2)CH(2))(2)PPh]) with AlCl(3) or GaCl(3) in toluene at 25 degrees C leads to the formation of the four-coordinate species anti-MCl[P(2)N(2)] (M = Al (1), Ga (2)). An X-ray diffraction study of anti-GaCl[P(2)N(2)] shows it to be monomeric with a distorted tetrahedral geometry at Ga; only one of the phosphine donors of the [P(2)N(2)] ligand binds to the gallium, resulting in the retention of the anti-configuration. The solution NMR spectra are consistent with C(s)() symmetry. The addition of AlCl(3) or GaCl(3) to the macrocyclic ligand precursor syn-Li(2)(dioxane)[P(2)N(2)] in toluene at 25 degrees C yields the five-coordinate complexes syn-MCl[P(2)N(2)] (M = Al (3), Ga (4)). The X-ray crystal structure of syn-GaCl[P(2)N(2)] reveals a trigonal bipyramidal geometry about the metal atom, necessitating the coordination of both phosphorus atoms. The solution NMR spectra are consistent with a C(2)(v)() symmetric complex. Heating the anti complexes results in the clean conversion to the syn complexes, with pyramidal inversion observed at phosphorus. The kinetics of this inversion were studied by (1)H NMR spectroscopy and found to be first-order. Barriers to pyramidal inversion (DeltaG()) were calculated to be 29.1 and 30.1 kcal mol(-)(1) for the aluminum and gallium complexes, respectively; these barriers are approximately 2-3 kcal mol(-)(1) lower than that determined for the metal-free, protonated compounds anti- and syn-H(2)[P(2)N(2)]. It is suggested that the role that the metals play in this inversion, based on the values of DeltaG(), involves the large negative entropies of activation and thus help organize the transition state.

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Section: Resultssupporting

confidence: 64%

Pyramidal Inversion at Phosphorus Facilitated by the Presence of Proximate Lewis Acids. Coordination Chemistry of Group 13 Elements with the Macrocyclic Bis(amidophosphine) Ligand [P₂N₂] ([P₂N₂] = [PhP(CH₂SiMe₂NSiMe₂CH₂)₂PPh])

1998

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“…These values compare well to 2314 cm 21 [n P-H (m)] for {[Me 2 Ga] 4 [(m-PH) 2 (C 6 H 4 )] 2 } 12 and to 2343 cm 21 [n P-H (sym)] and 2335 cm 21 [n P-H (asym)] for the phosphinogallane trimer [Bu t 2 Ga(m-PH 2 )] 3 . 13 The gallium hydride IR bands at 1801 cm 21 [n Ga-H (vw)] and 1849 cm 21 [n Ga-H (vw)] of 1 are comparable to previously reported gallium hydride IR bands: Me 2 N-GaH 3 , 14 1829 cm 21 [n Ga-H (vw)]; [(PhCH 2 (Me) 2 NGaH 3 ], 15 1835 cm 21 (n Ga-H ) and (Et 2 O) 2 Li-[m-As(SiMe 3 ) 2 ] 2 GaH 2 , 16 1834 cm 21 . Similar to 1 which exhibits two Ga-H IR bands, the organometallic (mono)hydride K[Ga(H)(CH 2 SiMe 3 ) 3 ] also exhibits two Ga-H IR bands at 1915 cm 21 [n Ga-H (vw)] and 1840 cm 21 [n Ga-H (vw)].…”

supporting

confidence: 85%

Synthesis and molecular structure of an unusual –Ga–Ga–Ga– linked organometallic

Wei

Beck

et al. 2000

Chem. Commun.

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“…This is a common coordination mode with group 13 alkyls and hydrides, where the metal center requires only one more interaction to achieve pseudotetrahedral symmetry, e.g. the TMED adducts of trimethylaluminum, gallane, , and bis(tris(trimethylsilyl)methyl)gallium …”

Section: Resultsmentioning

confidence: 99%

An Unusual Coordination Mode in a Bis(dialkyldithiocarbamato)zinc(II) Adduct with N,N,N‘,N‘-Tetramethylethylenediamine: X-ray Crystal Structures of 2[MeⁱPrNCS₂]₂Zn·Me₂N(CH₂)₂NMe₂ and [MeⁱPrNCS₂]₂Zn·C₅H₅N

et al. 1997

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Gallane adducts of bifunctional Group V ligands; crystal structures of (GaH3)2(tmen) and (GaH3)2(dmpe)

Cited by 38 publications

References 7 publications

Pyramidal Inversion at Phosphorus Facilitated by the Presence of Proximate Lewis Acids. Coordination Chemistry of Group 13 Elements with the Macrocyclic Bis(amidophosphine) Ligand [P₂N₂] ([P₂N₂] = [PhP(CH₂SiMe₂NSiMe₂CH₂)₂PPh])

Pyramidal Inversion at Phosphorus Facilitated by the Presence of Proximate Lewis Acids. Coordination Chemistry of Group 13 Elements with the Macrocyclic Bis(amidophosphine) Ligand [P₂N₂] ([P₂N₂] = [PhP(CH₂SiMe₂NSiMe₂CH₂)₂PPh])

Synthesis and molecular structure of an unusual –Ga–Ga–Ga– linked organometallic

An Unusual Coordination Mode in a Bis(dialkyldithiocarbamato)zinc(II) Adduct with N,N,N‘,N‘-Tetramethylethylenediamine: X-ray Crystal Structures of 2[MeⁱPrNCS₂]₂Zn·Me₂N(CH₂)₂NMe₂ and [MeⁱPrNCS₂]₂Zn·C₅H₅N

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Gallane adducts of bifunctional Group V ligands; crystal structures of (GaH3)2(tmen) and (GaH3)2(dmpe)

Cited by 38 publications

References 7 publications

Pyramidal Inversion at Phosphorus Facilitated by the Presence of Proximate Lewis Acids. Coordination Chemistry of Group 13 Elements with the Macrocyclic Bis(amidophosphine) Ligand [P2N2] ([P2N2] = [PhP(CH2SiMe2NSiMe2CH2)2PPh])

Pyramidal Inversion at Phosphorus Facilitated by the Presence of Proximate Lewis Acids. Coordination Chemistry of Group 13 Elements with the Macrocyclic Bis(amidophosphine) Ligand [P2N2] ([P2N2] = [PhP(CH2SiMe2NSiMe2CH2)2PPh])

Synthesis and molecular structure of an unusual –Ga–Ga–Ga– linked organometallic

An Unusual Coordination Mode in a Bis(dialkyldithiocarbamato)zinc(II) Adduct with N,N,N‘,N‘-Tetramethylethylenediamine: X-ray Crystal Structures of 2[MeiPrNCS2]2Zn·Me2N(CH2)2NMe2 and [MeiPrNCS2]2Zn·C5H5N

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Pyramidal Inversion at Phosphorus Facilitated by the Presence of Proximate Lewis Acids. Coordination Chemistry of Group 13 Elements with the Macrocyclic Bis(amidophosphine) Ligand [P₂N₂] ([P₂N₂] = [PhP(CH₂SiMe₂NSiMe₂CH₂)₂PPh])

Pyramidal Inversion at Phosphorus Facilitated by the Presence of Proximate Lewis Acids. Coordination Chemistry of Group 13 Elements with the Macrocyclic Bis(amidophosphine) Ligand [P₂N₂] ([P₂N₂] = [PhP(CH₂SiMe₂NSiMe₂CH₂)₂PPh])

An Unusual Coordination Mode in a Bis(dialkyldithiocarbamato)zinc(II) Adduct with N,N,N‘,N‘-Tetramethylethylenediamine: X-ray Crystal Structures of 2[MeⁱPrNCS₂]₂Zn·Me₂N(CH₂)₂NMe₂ and [MeⁱPrNCS₂]₂Zn·C₅H₅N