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Reactions of Secondary Dithioxamides with [(η 6 ‐ p ‐cymene)RuCl(μ‐Cl)] 2 : The Role of Steric Hindrance on Amidic Nitrogen in Determining the Reaction Products
Author(s) -
Lanza Santo,
Bruno Giuseppe,
Nicolò Francesco,
Rotondo Archimede,
Tresoldi Giuseppe
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(20021)2002:1<65::aid-ejic65>3.0.co;2-s
Subject(s) - chemistry , isopropyl , steric effects , medicinal chemistry , bimetallic strip , p cymene , stereochemistry , dimer , olefin fiber , nuclear magnetic resonance spectroscopy , ruthenium , metal , organic chemistry , catalysis
The reactions of secondary dithioxamides H 2 R 2 DTO 1−11 [R = methyl 1 , ethyl 2 , n ‐propyl 3 , n ‐butyl 4 , isoamyl 5 , benzyl 6 , p ‐tolyl 7 , ( R )‐1‐phenylethyl 8 , ( R , S )‐1‐phenylethyl 9 , isopropyl 10 , cyclohexyl 11 ] with the chloride‐bridge dimer [(η 6 ‐ p ‐cymene)RuCl(μ‐Cl)] 2 complex readily afforded either bimetallic ruthenium complexes of formula [(η 6 ‐ p ‐cymene)RuCl 2 ](μ‐R 2 DTO) (R = methyl 12a , R = ethyl, 12b , R = n ‐propyl 12c ; R = n ‐butyl 12d ; R = isoamyl 12e ; R = benzyl 12f ; R = p ‐tolyl 12g ) or mononuclear “piano stool” geometry ion pairs {(η 6 ‐ p ‐cymene)RuCl(H 2 R 2 DTO) + ,(Cl − ) κ‐ S , S ′ Ru} [R = ( R )‐1‐phenylethyl, 13a ; R = ( R , S )‐1‐phenylethyl, 13b ; R = isopropyl, 13c ; R = cyclohexyl, 13d ]. The driving force of the reactions was the bulkiness of the R groups attached to dithioxamides, leading respectively from primary and aromatic N ‐bonded carbons to neutral bimetallic species 12a − g , or from secondary N ‐bonded carbons to monometallic 13a − d species. These latter compounds could be easily dehydrohalogenated to give neutral “piano stool” complexes [(η 6 ‐ p ‐cymene)RuCl(HR 2 DTO) κ‐ S , S ′ Ru] [R = ( R )‐1‐phenylethyl 14a ; R = ( R , S )‐1‐phenylethyl 14b ; R = isopropyl 14c ; R = cyclohexyl 14d ]. All complexes were characterised in solution by 1 H and 13 C{ 1 H} NMR spectroscopy. Complex 12f was also characterised by mass spectrometry, and 12g by solid state X‐ray crystallography.