Chini, Paolo

Longoni Giuliano, Heaton Brian T., Chini Paolo, J. Chem. Soc., Dalton Trans.,... 

GIULIANO LONGONI and PAOLO CHINI—Instituto di Chimica Generale dell Universita di Milano, 20133 Milano, Italy... 

The chemistry of the carbidocarbonyl clusters of cobalt and rhodium (none is known for iridium) is predominantly the work of Italian school of the late Paolo Chini and colleagues. The first rhodium cluster of this type to be reported was [Rh6C(CO)ls]2, 24 (59), isolated as a minor by-product in the synthesis of [Rh7(CO)t6]3- (and originally misformulated as [Rh3(CO)l0]-). The formation of 24 resulted from the reaction of [Rh7(CO)l6]3- with chloroform (the source of the carbon atom), present as an impurity in the reaction solvent, and 24 is now synthesized by this reaction [Eq. (17)]. 

Unequivocal proof for the existence of a six-coordinate H atom in an octahedral cluster was subsequently provided by us, in collaboration with Dr. Thomas F. Koetzle of Brookhaven National Laboratory and the late Professor Paolo Chini of the University of Milan, in a single-crystal neutron diffraction study of [HCo6(CO)ls] 246)... 

Paolo Chini began his work in the late 1950s with the characterization of cobalt carbonyl species involved in the hydroformylation of olefins with cobalt catalysts, and in the course of these studies developed improved synthetic methods for the known cobalt carbonyls Co2(CO)8 and Co4(CO)12 [132]. His next steps were the preparation of the heterometallic hydrido complex HFe-Co3(CO)i2 (isoelectronic to Co4(CO)12) and the corresponding anion [FeCo3(CO)12], both a novelty at that time, and of the new hexanuclear cobalt clusters [Co6(CO)15]2, [Co6(CO)14]4, and Co6(CO)16 [133-139]. This work was followed by the synthesis of carbido carbonyl cluster anions [Co6(CO)i4C], [Co6(CO)15C]2 and [Co8(CO)i8C]2, containing an interstitial... 

Fig. 4.15 Paolo Chini at the time when he became Professor of Inorganic Chemistry at the University of Milan (photo by courtesy from Professor Giuliano Longoni)...

Calderazzo, Prof. Paolo Chini Biographical Memoir, J. Organomet. Chem. 213, ix-xii (1981). 

The term cluster-breathing was suggested by the late Paolo Chini. ... 

These early measurements stimulated my interest in NMR spectroscopy, and, on moving to the University of Kent at Canterbury (1972), we were lucky to be able to buy the first Fourier Transform NMR spectrometer in the UK. This instrument was still based on an electromagnet ( H, 100 MHz) but allowed faster acquisition of NMR spectra and enabled the development of multinuclear NMR spectroscopy. This permitted me to start collaborating with Paolo Chini who had taken up an appointment at the University of Milan where he was developing metal carbonyl cluster chemistry. In Milan, Chini had access only to an IR spectrometer that aided the clean preparation and subsequent crystallisation of clusters, and, importantly, an X-ray diffractometer for their structural characterisation. 

The year was sadly marked by the death of Paolo Chini on February 1st, 1980. His major contributions to the field are described in a review of large metal carbonyl clusters published posthumously. The methods developed by Chini and his group for the synthesis of [Ru4(CO)ij], K2[Rh8(CO)i6C], and Naa[Rhi2-(COjsol are described in a new volume of Inorganic Syntheses which is dedicated to his memory. ... 

---