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Diversity of Isomerization Patterns and Protolytic Forms in Aminocarbene PdII and PtII Complexes Formed upon Addition of N,N'-Diphenylguanidine to Metal-Activated Isocyanides.
- Source :
-
Organometallics . 11/13/2017, Vol. 36 Issue 21, p4145-4159. 15p. - Publication Year :
- 2017
-
Abstract
- Reaction of the palladium(II) and platinum(II) isocyanide complexes cis-[MCl2(CNR)2] [M = Pd, R = C6H3(2,6-Me2) (Xyl), 2-Cl-6-MeC6H3, cyclohexyl (Cy), t-Bu, C(Me)2CH2(Me)3 (1,1,3,3-tetramethylbuth-1-yl abbreviated as tmbu); M = Pt, R = Xyl, 2-Cl-6-MeC6H3, Cy, t-Bu, and tmbu] with N,N'-diphenylguanidine (DPG) leads to DPG-derived metal-bound deprotonated acyclic diaminocarbene (ADC) species. This reaction occurs via a two-step process, involving the initial coupling of the guanidine with one of the isocyanides and leading to deprotonated monocarbene monochelated species, while the next addition grants the deprotonated bis-carbene bis-chelated metal compounds. DPG behaves as nucleophile, deprotonating base, and chelator. The addition of DPG proceeded with different regioselectivity depending on the metal center and, in a larger extent, on the substituent R in RNCs. The X-ray diffraction studies for the deprotonated mono- and bis-carbene complexes confirmed the regioisomerism of these species and allowed the identification of ADC protolytic forms stabilized in the solid-state. 1D (1H and 13C{1H}) and 2D (1H,1H-NOESY; 1H,15N-HSQC; 1H,15N-HMBC) solution NMR of the obtained systems demonstrated their configuration isomerism accompanied by prototropic tautomerism. Together, the solid-state and solution data provide an insight into the flexible character of ADC species. [ABSTRACT FROM AUTHOR]
- Subjects :
- *ISOMERIZATION
*ISOCYANIDES
*METALS
*X-ray diffraction
*CARBENES
Subjects
Details
- Language :
- English
- ISSN :
- 02767333
- Volume :
- 36
- Issue :
- 21
- Database :
- Academic Search Index
- Journal :
- Organometallics
- Publication Type :
- Academic Journal
- Accession number :
- 126263689
- Full Text :
- https://doi.org/10.1021/acs.organomet.7b00569