TY - JOUR
T1 - Mehrfachbindungen zwischen hauptgruppenelementen und übergangsmetallen. XXXI. Über ein- und zweikernige halogenorhenium(V)-komplexe
T2 - synthesen und strukturen
AU - Herrmann, Wolfgang A.
AU - Küsthardt, Ulrich
AU - Flöel, Martina
AU - Kulpe, Jürgen
AU - Herdtweck, Eberhardt
AU - Voss, Erdmuthe
PY - 1986/10/21
Y1 - 1986/10/21
N2 - The dinuclear oxorhenium complex of composition [(η5-C5Me5)ReO2]2 (1) is subject to clean cleavage upon treatment with aqueous hydrogen fluoride, chloride, and bromide, thus yielding the mononuclear halfsandwich complexes (η5-C5Me5)ReOX2 (X F, 2a; Cl, 2b; Br, 2c). The multistep mechanism of these reactions starts off with O-protonation of the Re2O2 core as demonstrated by an independent synthesis of the isolable ionic intermediate [(η5-C5Me5)2Re2(μ-OH)2O2][BF4]2 (5). A low-yield side product of the reaction of 1 with aqueous hydrochloric acid is the dinuclear complex [(η5-C5Me5)Re(μ-O)Cl2]2 (4). The dichloro complex 2b, is easily prepared by treating (η5-C5Me5)ReO3 with germanium dichloride (dioxane complex; GeCl2 · C4H8O2). The preparation of the diiodo derivative (η5-C5Me5)ReOI2 2d) has been achieved by photolysis of (η5-C5Me5)Re(CO)3 in the presence of iodosobenzene. The molecular and crystal structure of (η5-C5Me5)ReOCl2 (2b) has been determined by single crystal X-ray diffraction techniques. Action of trimethylaluminum upon the dibromorhenium(V) complex 2c yields the dimethyl derivatives (η5-C5Me5)ReO(CH3)2 and (η5-C5Me5)ReBr2(CH3)2 (6).
AB - The dinuclear oxorhenium complex of composition [(η5-C5Me5)ReO2]2 (1) is subject to clean cleavage upon treatment with aqueous hydrogen fluoride, chloride, and bromide, thus yielding the mononuclear halfsandwich complexes (η5-C5Me5)ReOX2 (X F, 2a; Cl, 2b; Br, 2c). The multistep mechanism of these reactions starts off with O-protonation of the Re2O2 core as demonstrated by an independent synthesis of the isolable ionic intermediate [(η5-C5Me5)2Re2(μ-OH)2O2][BF4]2 (5). A low-yield side product of the reaction of 1 with aqueous hydrochloric acid is the dinuclear complex [(η5-C5Me5)Re(μ-O)Cl2]2 (4). The dichloro complex 2b, is easily prepared by treating (η5-C5Me5)ReO3 with germanium dichloride (dioxane complex; GeCl2 · C4H8O2). The preparation of the diiodo derivative (η5-C5Me5)ReOI2 2d) has been achieved by photolysis of (η5-C5Me5)Re(CO)3 in the presence of iodosobenzene. The molecular and crystal structure of (η5-C5Me5)ReOCl2 (2b) has been determined by single crystal X-ray diffraction techniques. Action of trimethylaluminum upon the dibromorhenium(V) complex 2c yields the dimethyl derivatives (η5-C5Me5)ReO(CH3)2 and (η5-C5Me5)ReBr2(CH3)2 (6).
UR - http://www.scopus.com/inward/record.url?scp=0000583736&partnerID=8YFLogxK
U2 - 10.1016/0022-328X(86)80360-6
DO - 10.1016/0022-328X(86)80360-6
M3 - Artikel
AN - SCOPUS:0000583736
SN - 0022-328X
VL - 314
SP - 151
EP - 162
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1-2
ER -