Gallane-coordinated transition metal complexes and related compounds

Muraoka, Takako; Ueno, Keiji

doi:10.1016/j.ccr.2010.01.002

Cited by 14 publications

(6 citation statements)

References 95 publications

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“…While there is little account for TM···Ga interactions in 12 , 12-W again contains a shorter TM···Ga separation than what would be reasoned from inspection of the solid state structures 12-Cr and 12-Mo . 38 , 39 Complex 13 is noticeably similar to 6 in terms of the TM–H–M parameters. In both cases, the Cp centroid –Mn–H–M torsion angle is near 90° allowing for overlap of the M–H σ*-orbital with the HOMO of the Mn fragment.…”

Section: σ-Complexes (Tm←h–m)mentioning

confidence: 79%

“…Ueno and co-workers provided evidence that the η 2 :η 2 -coordination mode is not necessary for the stabilisation of σ-gallanes, and reported 12 and 13 . 38 , 39 These complexes were formed from displacement of THF or CO from group 6 transition metal carbonyls by GaH 3 ·quinuclidine. While there is little account for TM···Ga interactions in 12 , 12-W again contains a shorter TM···Ga separation than what would be reasoned from inspection of the solid state structures 12-Cr and 12-Mo .…”

Section: σ-Complexes (Tm←h–m)mentioning

confidence: 99%

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Magnesium, zinc, aluminium and gallium hydride complexes of the transition metals

Butler

Crimmin

2017

Chem. Commun.

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Section: σ-Complexes (Tm←h–m)mentioning

confidence: 79%

Section: σ-Complexes (Tm←h–m)mentioning

confidence: 99%

Magnesium, zinc, aluminium and gallium hydride complexes of the transition metals

Butler

Crimmin

2017

Chem. Commun.

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“…17). 32 s-Complexes of Lewis base adducts of alanes 33,34 and gallanes 35 have also been reported, with the first structurally characterized monomeric alane complex being the nickel cyclododeca-1,5,9-triene (cdt) derivative, (cdt)Ni(k 1 -HAlEt 2 Q) (Q = quinuclidine), 33 illustrated in Fig. 18.…”

Section: Class I L-x 3c-2e Bondsmentioning

confidence: 97%

“…Furthermore, compounds that feature more complex alane ligands, namely amidate, guanidate and b-diketimate derivatives, are also known. 38 Gallane s-complexes have also been synthesized, 35 as illustrated by the quinuclidine derivatives, (CO) 5 W(k 1 -H 3 GaQ) 39 and Cp*Mn(CO) 2 (k 1 -H 3 GaQ) (Fig. 19).…”

Section: Class I L-x 3c-2e Bondsmentioning

confidence: 99%

The occurrence and representation of three-centre two-electron bonds in covalent inorganic compounds

2012

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Although compounds that feature 3-centre 2-electron (3c-2e) bonds are well known, there has been no previous effort to classify the interactions according to the number of electrons that each atom contributes to the bond, in a manner analogous to the classification of 2-centre 2-electron (2c-2e) bonds as either normal covalent or dative covalent. This article provides an extension to the Covalent Bond Classification (CBC) method by categorizing 3c-2e interactions according to whether (i) the two electrons are provided by one or by two atoms and (ii) the central bridging atom provides two, one, or zero electrons. Class I 3c-2e bonds are defined as those in which two atoms each contribute one electron to the 3-centre orbital, while Class II 3c-2e bonds are defined as systems in which the pair of electrons are provided by a single atom. Class I and Class II 3c-2e interactions can be denoted by structure-bonding representations that employ the "half-arrow" notation, which also provides a convenient means to determine the electron count at a metal centre. In contrast to other methods of electron counting, this approach provides a means to predict metal-metal bond orders that are in accord with theory. For example, compounds that feature symmetrically bridging carbonyl ligands do not necessarily have to be described as "ketone derivatives" because carbon monoxide can also serve as an electron pair donor to two metal centres. This bonding description also provides a simple means to rationalize the theoretical predictions of the absence of M-M bonds in molecules such as Fe(2)(CO)(9) and [CpFe(CO)(2)](2), which are widely misrepresented in textbooks as possessing M-M bonds.

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“…The Fe–H1 and Ga–H1 bond distances were 1.60(4) and 1.67(5) Å, respectively. The Fe–H1–Ga bond angle (122(2) °) was comparable to those reported for the σ-gallane complexes ((OC) 5 M(H 3 Ga·quinuclidine); M = W, Mo, and Cr, 119–126°) with M–H–Ga 3-center-2-electron (3c-2e) bonding . The Fe–C2 bond distance (1.957(4) Å) was within the usual bond range observed for the Fe–C single bonds in Fe-pyridyl complexes (1.95–2.08 Å) .…”

Section: Results and Discussionmentioning

confidence: 99%

Syntheses and Structures of Gallyliron Complexes with Pyridine Ligands and Their Reactions with Methyl Acrylate

et al. 2021

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Reactions of gallyliron complexes Cp*(OC)2FeGaR2 (R = Cl (1), Mes (2); Cp*, η5-C5Me5; Mes, 2,4,6-Me3C6H2) with pyridine in C6D6 afforded pyridine-stabilized gallyl complexes Cp*(OC)2Fe{GaR2(py)} (R = Cl (3), Mes (5a); py, pyridine). Photoirradiation of dichlorogallyl complex 3 in the presence of excess pyridine in benzene proceeded via the substitution of a CO ligand with another pyridine to give Cp*(OC)(py)Fe{GaCl2(py)} (4). However, photoirradiation of dimesitylgallyl complex 2 in the presence of excess pyridine gave gallane(pyridyl)iron complex Cp*(OC)Fe{(η1-HGaMes2)(η1-2-C5H4N)} (6a) via CO elimination and oxidative addition of the C–H bond at the 2-position of the gallium-coordinated pyridine. X-ray crystal structure analysis of 6a revealed the formation of a 3-center-2-electron (3c2e) bond in the Fe–H–GaMes2 fragment. Reaction of 4 with methyl acrylate in toluene at 50 °C resulted in substitution of the pyridine ligand on the iron atom with the C=C bond, giving Cp*(OC)(η2-CH2=CHCO2Me)Fe{GaCl2(py)} (7). In contrast, the reaction of 6a with methyl acrylate in toluene at 100 °C afforded vinyliron complex Cp*(OC)2Fe(CH=CH2) (8) and 4-membered Ga2O2 cyclic gallane compound [Mes2GaOMe]2 (9) via cleavage of the Fe–Ga, C–O, and C–C bonds.

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Gallane-coordinated transition metal complexes and related compounds

Cited by 14 publications

References 95 publications

Magnesium, zinc, aluminium and gallium hydride complexes of the transition metals

Magnesium, zinc, aluminium and gallium hydride complexes of the transition metals

The occurrence and representation of three-centre two-electron bonds in covalent inorganic compounds

Syntheses and Structures of Gallyliron Complexes with Pyridine Ligands and Their Reactions with Methyl Acrylate

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