Spontaneous Oxidative Addition of σ‐SiSi Bonds at Gold

Gualco, Pauline; Ladeira, Sonia; Miqueu, Karinne; Amgoune, Abderrahmane; Bourissou, Didier

doi:10.1002/anie.201103719

Cited by 78 publications

(57 citation statements)

References 86 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…With the important finding that σ-SiSi, σ-SnSn and σ-CX bonds undergo spontaneously oxidative addition to a gold(I) center in an intramolecular fashion (supported by the above mentioned chelate assistance) [13,14], we became further interested in this reactivity. In order to investigate the generality of this process, we envisaged the study of intermolecular oxidative addition to gold(I) complexes.…”

Section: Research Objectives and Thesis Outlinementioning

confidence: 99%

General Introduction

Joost¹

2015

Synthesis and Original Reactivity of Copper and Gold Complexes

View full text Add to dashboard Cite

Section: Research Objectives and Thesis Outlinementioning

confidence: 99%

General Introduction

Joost¹

2015

Synthesis and Original Reactivity of Copper and Gold Complexes

View full text Add to dashboard Cite

“…This chelating approach was extrapolated to the coordination and activation of σ-SiSi bonds at Cu (I) and Au(I) [30,31]. In case of copper, this strategy led to the isolation of the first structurally characterized σ-complex of a coinage metal (Fig.…”

Section: Synthesis and Characterization Of Cu(i) Complexesmentioning

confidence: 99%

“…On the basis of steric and orbital grounds, the formation of σ-complexes is a priori less favorable with disilanes than with hydrosilanes [45], but it is likely that geometric factors also play a role in our systems (the σ-SiSi bond was included within the chelating ligand backbone, while the σ-SiH bond is necessarily external). Finally, as spontaneous oxidative addition of the σ-SiSi bond had been observed at gold [31], a similar process with the σ-SiH bond of the copper complex 3* and gold complex 7* was considered theoretically. The structures of the corresponding Cu (III) and Au(III) complexes were optimized, and oxidative addition of the σ-SiH bond was found to be strongly disfavored energetically in both cases (by 34.5 kcal/mol for 3* and 15.9 kcal/mol for 7*), in agreement with the experimental observations.…”

mentioning

confidence: 92%

“…The comparison of complexes 2, 3 and 7 provides further support for the participation of the σ-SiH bond in the coordination to copper, but not to gold. The bonding situation in the gold complex 7 contrasts with the oxidative addition process observed with the σ-SiSi bond to give a disilyl gold(III) complex [31]. In complex 7, the metal center accommodates a quasi-linear bis(phosphine)Au + arrangement.…”

mentioning

confidence: 95%

See 1 more Smart Citation

Copper: σ-SiH Coordination to Cu(I)

Joost

2015

Synthesis and Original Reactivity of Copper and Gold Complexes

View full text Add to dashboard Cite

This chapter gives firstly an introduction concerning σ-complexes and in particular σ-SiH complexes. Afterwards, the obtained results concerning the coordination of diphosphino-hydrosilanes to Cu(I) will be described. Introduction σ-Bond Coordination to Transition MetalsThe activation of σ-bonds by transition metals to undergo oxidative addition is a fundamental reaction in the field of coordination chemistry. Coordination of a σ-bond to a metal center to form a σ-complex is generally involved on the way to complete bond cleavage ( Fig. 2.1). Such complexes that may be observed or even isolated, play key roles as intermediates or transition states in oxidative addition processes.The field of σ-complexes evolved significantly following the pioneering studies of Kubas et al. [1,2] in 1980s. The finding that an intact dihydrogen molecule coordinates to a transition metal was at first highly debated [2], but the relevance of this discovery for transition metal-catalyzed bond activation processes was soon recognized and stimulated the field of coordination chemistry.The coordination of a σ-bond is nowadays well understood and can be considered as an early state of bond activation or "arrested oxidative addition" [3]. The precise understanding of the bonding interaction in a σ-complex is therefore of paramount importance for synthetic applications, as knowledge of structure and reactivity of such complexes will lead to more active and selective catalysts. The side-on coordination of σ-bonds has become a textbook example for weak metal-ligand interactions [4] and a number of complexes containing HH [2], HSi [3,[5][6][7][8] HB [9], HC [10][11][12], SiSi [13][14][15][16] and even CC [17][18][19] bonds has been characterized.A σ-complex can be described as a 3-center 2-electron interaction where a σ-bond acting as a 2-electron donor is coordinated in a slide-on fashion (η 2 ) to a metal, in close relationship to the Dewar-Chatt-Duncanson model that rationalizes the bonding interaction of an alkene (or an alkyne) to a metal center to form a π-complex. The σ-orbital of the ligand overlaps with a vacant metal d-orbital which leads to donation of electron density from the ligand to the metal. Furthermore, such a complex may be stabilized by backbonding, i.e. retrodonation of electron density from the metal to the ligand by interaction of a filled metal orbital of suitable symmetry with the σ*-orbital of the ligand ( Fig. 2. 2).In analogy to other 3-center 2-electron bonds involving p-block elements like in polyboranes or carbonium ions, the bonding situation of a σ-complex cannot be depicted by a single Lewis structure and is therefore also categorized as a "nonclassical interaction".Equally important and closely related to σ-complexes are agostic interactions. Originally, this weak bonding interaction was defined as the intramolecular 3-center 2-electron coordination of a CH-bond to a transition metal, i.e. the ligand coordinating to a metal center is tethered to a CH-bond that is interacting in a side-on fashion wit...

show abstract

“…However, the ability of gold(I) complexes to an undergo oxidative addition of s-bonds, such as S À S, Si À Si, Sn À Sn, and C(aryl) À X bonds, has been recently demonstrated in intramolecular [5] as well as intermolecular versions. [6] In particular, we recently reported that rationally designed twocoordinate cationic gold(I) complexes [(DPCb)Au] + (DPCb = diphosphino-carborane) with a bent PAuP angle (ca.…”

mentioning

confidence: 99%

Oxidative Addition of Carbon–Carbon Bonds to Gold

et al. 2015

Self Cite

View full text Add to dashboard Cite

The oxidative addition of strained CC bonds (biphenylene, benzocyclobutenone) to DPCb (diphosphino-carborane) gold(I) complexes is reported. The resulting cationic organogold(III) complexes have been isolated and fully characterized. Experimental conditions can be adjusted to obtain selectively acyl gold(III) complexes resulting from oxidative addition of either the C(aryl)C(O) or C(alkyl)C(O) bond of benzocyclobutenone. DFT calculations provide mechanistic insight into this unprecedented transformation.

show abstract

Spontaneous Oxidative Addition of σ‐SiSi Bonds at Gold

Cited by 78 publications

References 86 publications

General Introduction

General Introduction

Copper: σ-SiH Coordination to Cu(I)

Oxidative Addition of Carbon–Carbon Bonds to Gold

Contact Info

Product

Resources

About