Luca Rocchigiani

Dr. Luca Rocchigiani

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Research Focus & Metrics

Academic Career Length

19Years (2008-Present)

(Calculated once Scilit publication data is synced: current year − year of first publication + 1)

Representative Publications

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24 December 2013 in Journal of the American Chemical Society
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Journal Article
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LRLuca Rocchigiani
Luca Rocchigiani
Gianluca CiancaleoniGianluca Ciancaleoni
Gianluca Ciancaleoni
CZCristiano Zuccaccia
Cristiano Zuccaccia
AMAlceo Macchioni
Alceo Macchioni

28 November 2012 in Organometallics
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Journal Article
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ABAlberto Bucci
Alberto Bucci
ASArianna Savini
Arianna Savini
LRLuca Rocchigiani
Luca Rocchigiani
CZCristiano Zuccaccia
Cristiano Zuccaccia
SRSilvia Rizzato
Silvia Rizzato
AMAlceo Macchioni
Alceo Macchioni


30 November 2011 in European Journal of Inorganic Chemistry
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Journal Article
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CZCristiano Zuccaccia
Cristiano Zuccaccia
GBGianfranco Bellachioma
Gianfranco Bellachioma
Sandra BolañoSandra Bolaño
Sandra Bolaño
LRLuca Rocchigiani
Luca Rocchigiani
ASArianna Savini
Arianna Savini
AMAlceo Macchioni
Alceo Macchioni

4 June 2018 in Journal of the American Chemical Society
Verified
Journal Article
Open access
LRLuca Rocchigiani
Luca Rocchigiani
JFJulio Fernandez-Cestau
Julio Fernandez-Cestau
ICIsabelle Chambrier
Isabelle Chambrier
Peter HrobarikPeter Hrobarik
Peter Hrobarik
MBManfred Bochmann
Manfred Bochmann
The synthesis of new families of stable or at least spectroscopically observable gold(III) hydride complexes is reported, including anionic cis-hydrido chloride, hydrido aryl and cis-dihydride complexes. Reactions between (C^C)AuCl(PR3) and LiHBEt3 afford the first examples of gold(III) phosphino hydrides (C^C)AuH(PR3) (R = Me, Ph, p-tolyl; C^C = 4,4′-di-tert-butylbiphenyl-2,2′-diyl). The X-ray structure of (C^C)AuH(PMe3) was determined. LiHBEt3 reacts with (C^C)AuCl(py) to give [(C^C)Au(H)Cl] , whereas (C^C)AuH(PR3) undergoes phosphine displacement, generating the dihydride [(C^C)AuH2] . Monohydrido complexes hydroaurate dimethylacetylene dicarboxylate to give Z-vinyls. (C^N^C)Au pincer complexes give the first examples of gold(III) bridging hydrides. Stability, reactivity and bonding characteristics of Au(III)-H complexes crucially depend on the interplay between cis and trans-influence. Remarkably, these new gold(III) hydrides extend the range of observed NMR hydride shifts from δ 8.5 to +7 ppm. Relativistic DFT calculations show that the origin of this wide chemical shift variability as a function of the ligand depends on the different ordering and energy gap between “shielding” Au(dπ)-based orbitals and “deshielding” σ(Au-H)-type MOs, which are mixed to some extent upon inclusion of spin-orbit (SO) coupling. The resulting 1H hydride shifts correlate linearly with the DFT optimized Au-H distances and Au-H bond covalency. The effect of cis ligands follows a nearly inverse ordering to that of trans ligands. This study appears to be the first systematic delineation of cis ligand influence on M-H NMR shifts and provides the experimental evidence for the dramatic change of the 1H hydride shifts, including the sign change, upon mutual cis and trans ligand alternation.