TY - JOUR
T1 - Ruthenium(II) carbonyl complexes containing tertiary phosphine chalcogenide ligands of the type Ph3PX; X=O, S, Se
AU - Chutia, Pratap
AU - Kumari, Nandini
AU - Sharma, Manab
AU - Woollins, John Derek
AU - Slawin, Alexandra Martha Zoya
AU - Dutta, Dipak K
PY - 2004/5/27
Y1 - 2004/5/27
N2 - The reactions of polymeric complex [Ru(CO)(2)Cl-2](n) with triphenyl phosphine chalcogenide ligands Ph3PX; X = O(a), S(b), Se(c) in 1:1 (Ru:L ratio) molar ratio gives five-coordinate complexes of the type [Ru(CO)(2)Cl-2(Ph3PX)](1a-c) while 1:2 (Ru:2L ratio) molar ratio produces six-coordinate [RU(CO)(2)Cl-2(Ph3PX)(2)](2a-c) complexes. The complexes 1a-c and 2a-c exhibit two equally intense nu(CO) bands in the range 2059-1989 and 2050-1980 cm(-1), respectively, indicating cis-disposition of the two terminal carbonyl groups. The values of nu(CO) frequencies irrespective of the complexes, in general, follow the order: Ph3PO > Ph3PS > Ph3PSe which may be ascribed in terms of "Soft-Hard" (Ru(II)-O) and "Soft-Soft" (Ru(II)-S/Se) interactions. The nu(PX) bands of the complexes observed in the range 1173-538 cm(-1) are 19-41 cm(-1) lower than those of the corresponding free ligands indicating the formation of Ru-X bonds. The molecular structure of the complex [Ru(CO)(2)Cl-2(Ph3PS)(2)] was determined by single X-ray crystallography. The crystal is monoclinic, space group Cc; a = 11.4990 Angstrom. b = 17.3966 Angstrom, c = 18.4788 Angstrom; alpha = 90degrees, beta = 98.160degrees, 90degrees. In the molecule, the Ru(II) atom occupies the center of a slightly distorted octahedral geometry which consists of two trans-S atoms of two Ph3PS ligands, two cis-CO groups and two cis-chlorides. The complexes have also been characterized by elemental analysis, H-1, C-13 and P-31 NMR spectroscopy. (C) 2004 Elsevier Ltd. All rights reserved.
AB - The reactions of polymeric complex [Ru(CO)(2)Cl-2](n) with triphenyl phosphine chalcogenide ligands Ph3PX; X = O(a), S(b), Se(c) in 1:1 (Ru:L ratio) molar ratio gives five-coordinate complexes of the type [Ru(CO)(2)Cl-2(Ph3PX)](1a-c) while 1:2 (Ru:2L ratio) molar ratio produces six-coordinate [RU(CO)(2)Cl-2(Ph3PX)(2)](2a-c) complexes. The complexes 1a-c and 2a-c exhibit two equally intense nu(CO) bands in the range 2059-1989 and 2050-1980 cm(-1), respectively, indicating cis-disposition of the two terminal carbonyl groups. The values of nu(CO) frequencies irrespective of the complexes, in general, follow the order: Ph3PO > Ph3PS > Ph3PSe which may be ascribed in terms of "Soft-Hard" (Ru(II)-O) and "Soft-Soft" (Ru(II)-S/Se) interactions. The nu(PX) bands of the complexes observed in the range 1173-538 cm(-1) are 19-41 cm(-1) lower than those of the corresponding free ligands indicating the formation of Ru-X bonds. The molecular structure of the complex [Ru(CO)(2)Cl-2(Ph3PS)(2)] was determined by single X-ray crystallography. The crystal is monoclinic, space group Cc; a = 11.4990 Angstrom. b = 17.3966 Angstrom, c = 18.4788 Angstrom; alpha = 90degrees, beta = 98.160degrees, 90degrees. In the molecule, the Ru(II) atom occupies the center of a slightly distorted octahedral geometry which consists of two trans-S atoms of two Ph3PS ligands, two cis-CO groups and two cis-chlorides. The complexes have also been characterized by elemental analysis, H-1, C-13 and P-31 NMR spectroscopy. (C) 2004 Elsevier Ltd. All rights reserved.
KW - ruthenium(II) carbonyl complexes
KW - tertiary phosphine chalcogenides
KW - "Soft-Hard" and "Soft-Soft" interactions
KW - X-ray crystal structure
KW - octahedral structure
KW - CATALYTIC-ACTIVITY
KW - CATIONIC RHODIUM(I)
KW - METAL CARBONYLS
KW - TRIPHENYLPHOSPHINE
KW - METHANOL
KW - RU(CO)2L2X2
KW - SULFIDES
KW - ISOMERS
KW - OXIDES
UR - http://www.scopus.com/inward/record.url?scp=2442536924&partnerID=8YFLogxK
UR - http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6TH8-4C76B50-3&_user=1026342&_coverDate=05%2F27%2F2004&_alid=178666451&_rdoc=1&_fmt=full&_orig=search&_cdi=5276&_sort=d&_st=4&_docanchor=&_acct=C000050565&_version=1&_urlVersion=0&_userid=1026342&md5=2d8f451b11baa4e1dacda6afd0319080
U2 - 10.1016/j.poly.2004.03.016
DO - 10.1016/j.poly.2004.03.016
M3 - Article
SN - 0277-5387
VL - 23
SP - 1657
EP - 1661
JO - Polyhedron
JF - Polyhedron
IS - 9
ER -