Vinyltrifluoroborate Complexes of Silver Supported by <i>N</i>‐Heterocyclic Carbenes

Wang, Guocang; Pecher, Lisa; Frenking, Gernot; Dias, H. V. Rasika

doi:10.1002/ejic.201800899

Cited by 15 publications

(11 citation statements)

References 110 publications

(116 reference statements)

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“…[34] In contrast, examples of crystallographically characterised linear Cu I and Ag I alkene complexes are extremely rare (Figure 1). [35,36] The paucity of data has meant that the comparison of bonding in ac omplete series of alkene complexes of the group 11 triad has not been possible.There is limited experimental evidence to show how modulation of the metal influences alkene binding,i ncluding the ability to adopt h 2 or h 1 coordination modes believed to be so important in key bond making steps during catalysis.…”

Section: Introductionmentioning

confidence: 99%

Group 11 Borataalkene Complexes: Models for Alkene Activation

et al. 2021

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A series of linear late transition metal (M=Cu, Ag, Au and Zn) complexes featuring a side‐on [B=C]− containing ligand have been isolated and characterised. The [B=C]− moiety is isoelectronic with the C=C system of an alkene. Comparison across the series shows that in the solid‐state, deviation between the η2 and η1 coordination mode occurs. A related zinc complex containing two [B=C]− ligands was prepared as a further point of comparison for the η1 coordination mode. The bonding in these new complexes has been interrogated by computational techniques (QTAIM, NBO, ETS‐NOCV) and rationalised in terms of the Dewar–Chatt–Duncanson model. The combined structural and computational data provide unique insight into catalytically relevant linear d10 complexes of Cu, Ag and Au. Slippage is proposed to play a key role in catalytic reactions of alkenes through disruption and polarisation of the π‐system. Through the preparation and analysis of a consistent series of group 11 complexes, we show that variation of the metal can impact the coordination mode and hence substrate activation.

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Section: Introductionmentioning

confidence: 99%

Group 11 Borataalkene Complexes: Models for Alkene Activation

et al. 2021

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“…Furthermore, to our knowledge, mercury(II) complexes of anionic N -herterocyclic carbene ligands, such as maloNHC, have not been investigated. As a continuation of our interest in the NHCs and their metal chemistry [ 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 ], we have set out to probe the use of anionic N -heterocyclic carbene ligands in mercury chemistry. In particular, we describe the synthesis and spectroscopic data of three new mercury(II) complexes ( Figure 1 ), (Me-maloNHC Dipp )HgCl ( 1b ), ( t -Bu-maloNHC Dipp )HgCl ( 2b ) and ( t -Bu-maloNHC Dipp )HgMe ( 2c ), involving a bulkier maloNHC.…”

Section: Introductionmentioning

confidence: 99%

Mercury(II) Complexes of Anionic N-Heterocyclic Carbene Ligands: Steric Effects of the Backbone Substituent

2020

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Mercury(II) complexes (Me-maloNHCDipp)HgCl (1b), (t-Bu-maloNHCDipp)HgCl (2b) and (t-Bu-maloNHCDipp)HgMe (2c) supported by anionic N-heterocyclic carbenes have been obtained in good yields from the reaction of the potassium salt of N-heterocyclic carbene ligand precursors and mercury(II) salts, HgCl2 and MeHgI. These molecules have been characterized by 1H-NMR, 13C-NMR and IR spectroscopy and elemental analysis. X-ray crystal structures of 1b and 2b are also presented. Interestingly, complex 1b is polymeric {(Me-maloNHCDipp)HgCl}n in the solid state, as a result of inter-molecular Hg-O contacts, and features rare three coordinate mercury sites with a T-shaped arrangement, whereas the (t-Bu-maloNHCDipp)HgCl (2b) is monomeric and has a linear, two-coordinate mercury center. The formation of T-shaped structure and the aggregation of complex 1b is attributable to the reduced steric demand of the N-heterocyclic carbene ligand backbone substituent.

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“…The 13 C{ 1 H} NMR signal of the copper bound C̲ H 2 vCHBF 3 could be observed as a singlet at δ 99.9 ppm for (SIPr)Cu(MeCN)(CH 2 vCHBF 3 ). 6 and K(CH 2 vCHBF 3 ) 13 which are observed at δ 114.3, 120.1 and 121.6 ppm, respectively. Thus, the copper(I) coordination has a more significant effect on the [CH 2 vCHBF 3 ] − group.…”

Section: Resultsmentioning

confidence: 98%

“…9 Recently, we have reported the isolation of silver complexes (SIPr)Ag(CH 2 vCHBF 3 ) ( 3) and (IPr*)Ag(CH 2 vCHBF 3 ) of this interesting ligand. 6 Furthermore, the calculated metal-ligand binding energies show that [CH 2 vCHBF 3 ] − is a significantly better ligand for Ag(I) than CH 2 vCH 2 or the isoelectronic CH 2 vCHCF 3 . Here we describe an extension of that effort to uncover the copper complexes, compare the copper and silver chemistry, and computationally study the vinyltrifluoroborates of Cu, Ag and Au in detail.…”

Section: Introductionmentioning

confidence: 96%

“…1), 4 a phenyltrifluoroborate adduct of ruthenium, 2, 5 and (SIPr)Ag(CH 2 vCHBF 3 ) ( 3) and (IPr*)Ag (CH 2 vCHBF 3 ) (SIPr = 1,3-bis (2,6-diisopropylphenyl)imidazolin-2-ylidene); IPr* = 1,3-bis (2,6-bis(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene) featuring a vinyltrifluoroborate ligand on silver(I) supported by N-heterocyclic carbenes (NHCs). 6 As a part of our ongoing activities involving metal-olefin complexes, 7 we became interested in the coordination chem-Fig. 1 Organotrifluoroborate complexes of transition metal ions.…”

Section: Introductionmentioning

confidence: 99%

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