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Reactivity of [Ge 9 {Si(SiMe 3 ) 3 } 3 ] − Towards Transition‐Metal M 2+ Cations: Coordination and Redox Chemistry
Author(s) -
Kysliak Oleksandr,
Schrenk Claudio,
Schnepf Andreas
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201603441
Subject(s) - transition metal , chemistry , crystallography , redox , nickel , reactivity (psychology) , cluster (spacecraft) , metal , metathesis , electron paramagnetic resonance , metalloid , atom (system on chip) , open shell , inorganic chemistry , stereochemistry , catalysis , polymer , organic chemistry , medicine , alternative medicine , physics , pathology , nuclear magnetic resonance , computer science , embedded system , polymerization , programming language
Recently the metalloid cluster compound [Ge 9 Hyp 3 ] − ( 1 ; Hyp=Si(SiMe 3 ) 3 ) was oxidatively coupled by an iron(II) salt to give the largest metalloid Group 14 cluster [Ge 18 Hyp 6 ]. Such redox chemistry is also possible with different transition metal (TM) salts TM 2+ (TM=Fe, Co, Ni) to give the TM + complexes [Fe(dppe) 2 ][Ge 9 Hyp 3 ] ( 3 ; dppe=1,2‐bis(diphenylphosphino)ethane), [Co(dppe) 2 ][Ge 9 Hyp 3 ] ( 4 ), [Ni(dppe)(Ge 9 Hyp 3 )] ( 5 ) and [Ni(dppe) 2 (Ge 9 Hyp 3 )] + ( 6 ). Such a redox reaction does not proceed for Mn, for which a salt metathesis gives the first open shell [Hyp 3 Ge 9 ‐M‐Ge 9 Hyp 3 ] cluster ( 2 ; M=Mn). The bonding of the transition metal atom to 1 is also possible for Ni (e.g., compound 6 ), in which one or even two nickel atoms can bind to 1 . In contrast to this in case of the Fe and Co compounds 3 and 4 , respectively, the transition‐metal atom is not bound to the Ge 9 core of 1 . The synthesis and the experimentally determined structures of 2 – 6 are presented. Additionally the bonding within 2 – 6 is analyzed and discussed with the aid of EPR measurements and quantum chemical calculations.