Structural, Theoretical and Spectroscopic Characterisation of a Series of Novel Gold(I)‐Norbornene Complexes Supported by Phenanthrolines: Effects of the Supporting Ligand

Abstract

A series of novel gold(I) alkene complexes of general formula [Au(N^N)(η 2 -nb)][PF 6 ] [N^N = PHEN (1,10-phenanthroline), NCP (2,9-dimethyl-1,10-phenanthroline), 4,7-DMP (4,7-dimethyl-1,10-phenanthroline), TMP (3,4,7,8-tetramethyl-1,10phenanthroline), BTP (4,7-diphenyl-1,10-phenanthroline) and BTC (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline); nb = norbornene] were synthesized by a novel synthetic pathway. The novel cationic gold(I)-norbornene complexes were fully characterized by 1 H and 13 C NMR spectroscopy and the crystal structure of three complexes was solved by single-crystal X-ray dif- [a] Synthesis and CharacterizationThe hexafluorophosphate salts of the new three-coordinate gold(I) norbornene complex cations [Au(N^N)(η 2 -nb)] + [N^N = PHEN (1,10-phenanthroline) (1-PF 6 ), NCP (2,9-dimethyl-1,10-Scheme 1. General structure of the nb complexes [Au(N^N)(η 2 -nb)][PF 6 ] (1-PF 6 -6-PF 6 ) and of the N^N ligands.

Versatility and adaptative behaviour of the P^N chelating ligand MeDalphos within gold(i) π complexes

“…The bonding situation within [(2,2′-bipy)Au(ethylene) + ] 8 b was investigated in 2006 and very recently, calculations were carried out on [(phenanthroline)Au(norbornene) + ] complexes. 14 …”

The 9‐Borataphenanthrene Anion

“…The nucleophilicity at carbon and addition reactivity with HBpin provide evidence for a borataalkene description of 1 . Given the resemblance of the HOMO on the B=C bond to the HOMO of an olefin, we postulated that η 2 coordination with the π‐bond could occur, reminiscent of an olefin . Reaction of 1 with (Ph 3 P)AuCl at room temperature resulted in a color change from yellow to colorless (Scheme ), and in situ 31 P{ 1 H} NMR spectroscopy showed the emergence of a singlet at 39.7 ppm along with the disappearance of the singlet at 33.2 ppm corresponding to (Ph 3 P)AuCl with the reaction complete in an hour.…”

“…[8,80,81] Given the resemblance of the HOMO on the B=C bond to the HOMO of an olefin, we postulated that h 2 coordination with the p-bond could occur,r eminiscent of an olefin. [82][83][84] Reaction of 1 with (Ph 3 P)AuCl at room temperature resulted in ac olor change from yellow to colorless (Scheme 4), and in situ 31 P{ 1 H} NMR spectroscopy showed the emergence of as inglet at 39.7 ppm along with the disappearance of the singlet at 33.2 ppm corresponding to (Ph 3 P)AuCl with the reaction complete in an hour. Theinsitu 11 BNMR spectrum contained as ingle broad peak at 42.4 ppm, slightly downfield from 1 (40.4 ppm).…”

Can Serendipity Still Hold Any Surprises in the Coordination Chemistry of Mixed-Donor Macrocyclic ligands? The Case Study of Pyridine-Containing 12-Membered Macrocycles and Platinum Group Metal ions PdII, PtII, and RhIII

“…Within the variety of DFT methods available, the broken symmetry approach (DFT-BS) proposed by Noodleman [65][66][67], widely used in the field of molecular magnetism for the calculation of ex- Theoretical calculations carried out at the Density Functional Theory (DFT) [56] level represent an invaluable tool in understanding the electronic structure of metal complexes. They have been extensively used by chemists to investigate structure/property relationships in a large variety of compounds, in fields as varied as material science and bioinorganic chemistry [57][58][59][60], including metal•••metal interactions [61][62][63][64]. Within the variety of DFT methods available, the broken symmetry approach (DFT-BS) proposed by Noodleman [65][66][67], widely used in the field of molecular magnetism for the calculation of exchange coupling constants in multinuclear complexes [68], allows unrestricted calculations for low-spin open-shell molecular systems, in which the α and β electrons are allowed to be localized on different atomic centers.…”