Synthesis and Comparative Study of the Physicochemical Properties of the Related Optically Active Complexes
[(μ-H)Os3{μ-OCNH-(R)-CHMePh} (CO)9L]{L=CO, NMe3, (S)-(-)-, or (R)-(+)-NH 2CHMePh}, Toward the Cluster and Amino Ligand Configuration Determination
Full article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| Journal |
Tetrahedron: Asymmetry
ISSN: 0957-4166
, E-ISSN: 1362-511X
|
| Output data |
Year: 2004,
Volume: 15,
Number: 1,
Pages: 109-118
Pages count
: 10
DOI:
10.1016/j.tetasy.2003.11.012
|
| Authors |
Ershova Victoria A.
,
Pogrebnyak Vladimir M.
,
Golovin Anatoly V.
,
Virovets Alexander V.
,
Semyannikov Peter P.
|
| Affiliations |
| 1 |
Nikolaev Institute of Inorganic Chemistry SB RAS
|
|
Funding (2)
|
1
|
Russian Foundation for Basic Research
|
01-03-32426
|
|
2
|
Russian Foundation for Basic Research
|
03-03-06628
|
A series of eight related optically active complexes having two or three stereogenic centers, [(l-H)Os3{l-OCNH-(R)-
CHMePh}(CO)10], 1, and [(l-H)Os3{l-OCNH-(R)-CHMePh}(CO)9L] {L ¼ NMe3, 2, and (S)-())- or (R)-(+)-NH2CHMePh, 3},
have been prepared and characterized by 1H and 13C NMR, IR, mass-spectral, and [α]D data. As shown by comparison of 1H NMR spectra in the highly informative upfield region, the relative values of dl-H for corresponding diastereomers depend on a number of stereogenic centers in the molecule, the nature of L (CO or amine) and solvent and most of all on the absolute configuration of the cluster fragment [HOs3(l-OCN)]. The relative positions of hydride signals in 1H NMR spectra of the diastereomeric pairs 1–3 correlates with the cluster-fragment configuration. The largest value of nonequivalence Ddl-H (0.36 ppm) was demonstrated by the diastereomers having the opposite cluster-fragment configurations and L ¼ (S)-())-NH2CHMePh in CDCl3 solution.