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Acetylene Dithiolate Linking up the [Tp′W(CO)(CN)] Moiety with Ru II or Pd II
Author(s) -
Seidel Wolfram W.,
Dachtler Woldemar,
Semmler Julia,
Tänzler Marco,
Folk Manuel,
Villinger Alexander
Publication year - 2013
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.201301192
Subject(s) - moiety , chemistry , acetylene , transition metal , alkyne , stereochemistry , crystallography , medicinal chemistry , ruthenium , metal , crystal structure , catalysis , organic chemistry
A series of heterodinuclear complexes with acetylene dithiolate (acdt 2− ) as the bridging moiety were synthesised by a facile one‐pot procedure that avoided use of the highly elusive acetylene dithiol. Generation of the W–Ru complex [Tp′W(CN)(CO)(C 2 S 2 )Ru(η 5 ‐C 5 H 5 )(PPh 3 )] (Tp’=hydrotris(3,5‐dimethylpyrazolyl)borate) and the W–Pd complexes [Tp′W(CN)(CO)(C 2 S 2 )Pd(dppe)] and [Tp′W(CO) 2 (C 2 S 2 )Pd(dppe)][PF 6 ] (dppe=1,2‐bis(diphenylphoshino)ethane), which exhibit a [W(η 2 ‐κ 2 ‐C 2 S 2 )M] core (M=Ru, Pd), was accomplished by using a transition‐metal‐assisted solvolytical removal of the Me 3 Si‐ethyl thiol protecting groups. All intermediate species of the reaction have been fully characterised. The highly coloured W–Ru complex [Tp′W(CN)(CO)(C 2 S 2 )Ru(η 5 ‐C 5 H 5 )(PPh 3 )] shows reversible redox chemistry, as does the prototype complex [Tp′W(CO) 2 (C 2 S 2 )Ru(η 5 ‐C 5 H 5 )(PPh 3 )][PF 6 ]. Single crystal X‐ray diffraction and IR, EPR and UV/Vis spectroscopic studies in conjunction with DFT calculations prove the high electronic delocalisation of states over the acdt 2− linker. Comparative studies revealed a higher donor strength and more pronounced dithiolate character of acdt 2− in [Tp′W(CN)(CO)(C 2 S 2 )Ru(η 5 ‐C 5 H 5 )(PPh 3 )] relative to [Tp′W(CO) 2 (C 2 S 2 )Ru(η 5 ‐C 5 H 5 )(PPh 3 )] + . In addition, the influence of the overall complex charge on the metric parameters was investigated by single‐crystal X‐ray diffraction studies with the W–Pd complexes [Tp′WL 2 (C 2 S 2 )Pd(dppe)] (L=(CN − )(CO) or (CO) 2 ). The central [W(C 2 S 2 )Pd] units exhibit high structural similarity, which indicates the extensive delocalisation of charge over both metals.