Partially fluorinated Scorpionate [HB(3-(CF3),5-(Ph)Pz)3]− as a supporting ligand for silver(I)-benzene, -carbonyl, and -PPh3 complexes

Ridlen, Shawn G.; Kulkarni, Naveen V.; Dias, H. V. Rasika

doi:10.1016/j.poly.2016.09.014

Cited by 8 publications

(7 citation statements)

References 70 publications

(55 reference statements)

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“…The carbonyl and isocyanide complexes were chosen for this study not only because of their importance ,− but also since their CO and CN stretch could serve as a gauge of ligand electronic effects on the metal sites . It is noteworthy that isolable silver carbonyl complexes are also quite rare. ,,− …”

Section: Introductionmentioning

confidence: 99%

Carbonyl and Isocyanide Complexes of Copper and Silver Supported by Fluorinated Poly(pyridyl)borates

Vanga

Noonikara‐Poyil

et al. 2022

Organometallics

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The pyridine-based poly(pyridyl)borates are a recent addition to the scorpionate family. Furthermore, pyridyl ring substituted analogues are also rare. The synthesis of a bis(pyridyl)borate featuring trifluoromethyl substituted pyridyl donor arms and its utility in isocyanide and carbonyl chemistry of copper(I) and silver(I) have been described together with related molecules supported by a fluorinated tris(pyridyl)borate, and a comparison to the better-known poly(pyrazolyl)borate relatives. X-ray crystal structures of copper and silver complexes show that the B-arylated, bis-and tris(pyridyl)borate ligands use only two pyridyl moieties for metal ion coordination. Flanking B-aryl groups close to metal sites are also a common feature in copper and silver complexes supported by [Ph 2 B(6-(CF 3 )Py) 2 ] − and [t-BuC 6 H 4 B(6-(CF 3 )Py) 3 ] − . The CN stretching frequencies of the t-BuNC complexes of Cu(I) and Ag(I) are notably higher than that of the free t-BuNC. The CO stretch of the analogous fluorinated poly(pyridyl)borate ligand supported metal carbonyls lies closer to that of the free CO, indicating the presence of fairly Lewis acidic metal sites. Metal bound carbonyl stretching frequencies of comparable poly(pyridyl)borate and poly(pyrazolyl)borate have been utilized to gauge the relative donor properties of the two ligand families.

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Section: Introductionmentioning

confidence: 99%

Carbonyl and Isocyanide Complexes of Copper and Silver Supported by Fluorinated Poly(pyridyl)borates

Vanga

Noonikara‐Poyil

et al. 2022

Organometallics

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“…Figure 2 shows the Ag(I)CO complexes that were selected for this study. They include the experimentally characterized tris(pyrazolyl)borate complexes 2 , 34,37 3 , 43 4 , 80 5 , 45 7 , 40 8 39 and the related 1,2,4‐triazolylborate complex 6 41 . For completeness, we also considered the parent complex 1 and the cationic tris(pyrazolyl)methane analogues 9 and 10 where the boron atom was replaced by a carbon atom for comparison reasons.…”

Section: Resultsmentioning

confidence: 99%

“… 33 We demonstrated the utility of tris(pyrazolyl)borate in this chemistry and the isolation of [HB(3,5‐[CF 3 ] 2 Pz) 3 ]Ag(CO) ( B ) 34 . Since then, a few other silver carbonyl complexes including some with X‐ray structural data have appeared in the literature, but they are still quite limited 35–45 …”

Section: Introductionmentioning

confidence: 99%

“…34 Since then, a few other silver carbonyl complexes including some with X-ray structural data have appeared in the literature, but they are still quite limited. [35][36][37][38][39][40][41][42][43][44][45] The most striking feature of these silver(I) carbonyl complexes is that almost all exhibit CO stretching frequency values greater than that for the free CO molecule, 2143 cm À1 . In fact, ν(CO) of Ag(CO)B (OTeF 5 ) 4 (2204 cm À1 ) is one of the highest reported for any transition metal carbonyl complex.…”

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confidence: 99%

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Bonding situation in isolable silver(I) carbonyl complexes of the Scorpionates

2022

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The bonding situation of Ag(I)CO complexes having a Scorpionate ligand directly attached to the transition metal has been analyzed in detail by means of relativistic density functional theory calculations. To this end, different experimentally characterized complexes together with other representative species have been considered to rationalize the observed shift of the corresponding ν(CO) stretching frequencies and the influence of the substituents in the Scorpionate ligand. With the help of the energy decomposition analysis method combined with the natural orbital for chemical valence it is found that the main contribution to the bonding comes from the electrostatic attractions between the LAg(I) and CO fragments. Despite that, the LAg → CO π‐backdonation is also significant in these species as well as in related LCu(I)CO complexes.

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“…Such complexes are particularly useful for further studies because tris(pyrazolyl)borate ligands and the properties of their metal complexes are easily tunable through various substituents on the pyrazolyl arms. For example, [HB(3,5-(CF 3 ) 2 Pz) 3 ]Ag(CO) 10 and [HB(3-(CF 3 ),5-(Ph)Pz) 3 ]Ag(CO) 11 display their ν (CO) at 2178 and 2148 cm −1 , respectively, significantly affecting the C–O stretch with respect to free CO (2143 cm −1 ), as a result of changing the pyrazolyl ring substituents on the tris(pyrazolyl)borate ligand. It is even possible to obtain rare Ag–CO complexes with the ν (CO) lower than that of the free CO (“classical carbonyls” in contrast to the “non-classical” silver-carbonyls noted above) 12 through the manipulation of substituents as in [MeB(3-(Mes)Pz) 3 ]Ag(CO) ( ν (CO) = 2125 cm −1 ).…”

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confidence: 99%