TY - JOUR
T1 - Synthesis, structure, and reactivity of (η5: η1-C5Me4(CH2) 2NMe2)Re(CO)2. Electron transfer behavior of a nitrosyl derivative
AU - Godoy, Fernando
AU - Gómez, Alejandra
AU - Segura, Rodrigo
AU - Doctorovich, Fabio
AU - Pellegrino, Juan
AU - Gaviglio, Carina
AU - Guerrero, Paulina
AU - Klahn, A. Hugo
AU - Fuentealba, Mauricio
AU - Garland, María Teresa
N1 - Funding Information:
We thank the “ Fondo de Desarrollo Científico y Tecnológico ” (FONDECYT) Chile ( 1110838 ), for financial support under project N° 1110838. A.G. acknowledge CONICYT for a doctoral fellowship. This work was also financially supported by UBA ( UBACYT W583 and 2010-12), ANPCyT (PICT 2010-2649 and 2010-416 ), CONICET ( PIP1207 and 112-201001-00125 ) and from the Bunge y Born Foundation . FD is member of CONICET. The OTTLE cell was kindly provided by Prof. Dr. Wolfgang Kaim.
PY - 2014/8/15
Y1 - 2014/8/15
N2 - The UV irradiation of a hexane solution of the complex (η5- C5Me4(CH2)2NMe2)Re(CO) 3 (1) afforded the chelated species (η5: η1-C5Me4(CH2) 2NMe2)Re(CO)2 (2). The molecular structure of 2 has been determined by X-ray crystallography. The reaction of 2 with two-electron donor ligands yields (η5-C5Me 4(CH2)2NMe2)Re(CO)2(L) (1, L = CO; 3, L = PMe3). The chelated species 2 also reacts with MeOTf, HBF4, and I2 to form the cationic compounds trans-[(η5-C5Me4(CH2) 2NMe2)Re(CO)2X]+ ([4]+, X = Me; [5]+, X = H; [6]+, X = I). The trans stereochemistry of 4-6 have been assigned on the basis of ν(CO) IR intensities and 13C NMR spectroscopy. Also, complex 2 reacts with nitrosyl tetrafluoroborate to yield [(η5-C5Me 4(CH2)2NMe2NO)Re(CO) 2(NO)]BF4 ([7]2+). The redox behavior of the {ReNO}6 complex [7]2+ was studied and the products obtained after two-electron reduction were characterized by IR. DFT calculations were done to optimize the structure of [7]2+ and to study the effect of the sidearm coordination on the electronic structure of a cyclopentadienyl {ReNO}8 complex.
AB - The UV irradiation of a hexane solution of the complex (η5- C5Me4(CH2)2NMe2)Re(CO) 3 (1) afforded the chelated species (η5: η1-C5Me4(CH2) 2NMe2)Re(CO)2 (2). The molecular structure of 2 has been determined by X-ray crystallography. The reaction of 2 with two-electron donor ligands yields (η5-C5Me 4(CH2)2NMe2)Re(CO)2(L) (1, L = CO; 3, L = PMe3). The chelated species 2 also reacts with MeOTf, HBF4, and I2 to form the cationic compounds trans-[(η5-C5Me4(CH2) 2NMe2)Re(CO)2X]+ ([4]+, X = Me; [5]+, X = H; [6]+, X = I). The trans stereochemistry of 4-6 have been assigned on the basis of ν(CO) IR intensities and 13C NMR spectroscopy. Also, complex 2 reacts with nitrosyl tetrafluoroborate to yield [(η5-C5Me 4(CH2)2NMe2NO)Re(CO) 2(NO)]BF4 ([7]2+). The redox behavior of the {ReNO}6 complex [7]2+ was studied and the products obtained after two-electron reduction were characterized by IR. DFT calculations were done to optimize the structure of [7]2+ and to study the effect of the sidearm coordination on the electronic structure of a cyclopentadienyl {ReNO}8 complex.
KW - Cyclopentadienyl functionalized
KW - Nitrosyl
KW - Rhenium
UR - http://www.scopus.com/inward/record.url?scp=84901020418&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2014.04.019
DO - 10.1016/j.jorganchem.2014.04.019
M3 - Article
AN - SCOPUS:84901020418
SN - 0022-328X
VL - 765
SP - 8
EP - 16
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
ER -