TY - JOUR
T1 - A nucleophilic gold complex
AU - Hicks, Jamie
AU - Mansikkamäki, Akseli
AU - Vasko, Petra
AU - Goicoechea, Jose M.
AU - Aldridge, Simon
N1 - Publisher Copyright:
© 2019, The Author(s), under exclusive licence to Springer Nature Limited.
PY - 2019/3/1
Y1 - 2019/3/1
N2 - Solid-state auride salts featuring the negatively charged Au – ion are known to be stable in the presence of alkali metal counterions. While such electron-rich species might be expected to be nucleophilic (in the same manner as I – , for example), their instability in solution means that this has not been verified experimentally. Here we report a two-coordinate gold complex (NON)AlAuP t Bu 3 (where NON is the chelating tridentate ligand 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene) that features a strongly polarized bond, Au δ– –Al δ+ . This is synthesized by reaction of the potassium aluminyl compound [K{Al(NON)}] 2 with t Bu 3 PAuI. Computational studies of the complex, including quantum theory of atoms in molecules charge analysis, imply a charge at gold (−0.82) that is in line with the relative electronegativities of the two metals (Au: 2.54; Al: 1.61 on the Pauling scale). Consistently, the complex is found to act as a nucleophilic source of gold, reacting with diisopropylcarbodiimide and CO 2 to give the Au–C bonded insertion products (NON)Al(X 2 C)AuP t Bu 3 (X = N i Pr, 4; X = O, 5).
AB - Solid-state auride salts featuring the negatively charged Au – ion are known to be stable in the presence of alkali metal counterions. While such electron-rich species might be expected to be nucleophilic (in the same manner as I – , for example), their instability in solution means that this has not been verified experimentally. Here we report a two-coordinate gold complex (NON)AlAuP t Bu 3 (where NON is the chelating tridentate ligand 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene) that features a strongly polarized bond, Au δ– –Al δ+ . This is synthesized by reaction of the potassium aluminyl compound [K{Al(NON)}] 2 with t Bu 3 PAuI. Computational studies of the complex, including quantum theory of atoms in molecules charge analysis, imply a charge at gold (−0.82) that is in line with the relative electronegativities of the two metals (Au: 2.54; Al: 1.61 on the Pauling scale). Consistently, the complex is found to act as a nucleophilic source of gold, reacting with diisopropylcarbodiimide and CO 2 to give the Au–C bonded insertion products (NON)Al(X 2 C)AuP t Bu 3 (X = N i Pr, 4; X = O, 5).
UR - http://www.scopus.com/inward/record.url?scp=85060335510&partnerID=8YFLogxK
U2 - 10.1038/s41557-018-0198-1
DO - 10.1038/s41557-018-0198-1
M3 - Article
SN - 1755-4330
VL - 11
SP - 237
EP - 241
JO - Nature Chemistry
JF - Nature Chemistry
IS - 3
ER -