TY - JOUR
T1 - Multiple bonds between transition metals and main-group elements, 163 Nitrogen-donor adducts of organorhenium( VII) oxides
T2 - Structural and catalytic aspects
AU - Herrmann, Wolfgang A.
AU - Kühn, Fritz E.
AU - Mattner, Mike R.
AU - Artus, Georg R.J.
AU - Geisberger, Martin R.
AU - Correia, João D.G.
PY - 1997/6/20
Y1 - 1997/6/20
N2 - N-base adducts of methyltrioxorhenium(VII) (1), characterized by their structural and spectroscopic data, are compared with respect to the influence of the pKb values of the N-bases. The crystal structure of one of these derivatives, namely the adduct of Tröger's base ((5R,11R)-(+)-2,8-dimethyl-6H,12H-5,11-methanodibenzo[b,f]-[1,5]diazocine) with compound 1 (2a) is reported. The cell constants are as follows: a = 1281.6(2)pm, b = 833.9(1)pm, c = 1705.5(2)pm, β = 106.09(1)°, V = 1751.2(4)×106 pm3. Derivative 2a exhibits the longest Re(VII)-N bond distance known to date. Furthermore, 2a is the first adduct of Tröger's base whose structure has been examined by X-ray crystallography. Epoxidation and sulfoxidation catalysis with N-base adducts of 1 is described, the influence of the Re-N bond strength on the catalytic processes is discussed.
AB - N-base adducts of methyltrioxorhenium(VII) (1), characterized by their structural and spectroscopic data, are compared with respect to the influence of the pKb values of the N-bases. The crystal structure of one of these derivatives, namely the adduct of Tröger's base ((5R,11R)-(+)-2,8-dimethyl-6H,12H-5,11-methanodibenzo[b,f]-[1,5]diazocine) with compound 1 (2a) is reported. The cell constants are as follows: a = 1281.6(2)pm, b = 833.9(1)pm, c = 1705.5(2)pm, β = 106.09(1)°, V = 1751.2(4)×106 pm3. Derivative 2a exhibits the longest Re(VII)-N bond distance known to date. Furthermore, 2a is the first adduct of Tröger's base whose structure has been examined by X-ray crystallography. Epoxidation and sulfoxidation catalysis with N-base adducts of 1 is described, the influence of the Re-N bond strength on the catalytic processes is discussed.
KW - Catalysis
KW - Methyltrioxorhenium
KW - N-base adducts
KW - Olefin epoxidation
KW - Sulfoxidation
KW - Tröger's base
UR - http://www.scopus.com/inward/record.url?scp=0031580153&partnerID=8YFLogxK
U2 - 10.1016/S0022-328X(96)06919-7
DO - 10.1016/S0022-328X(96)06919-7
M3 - Article
AN - SCOPUS:0031580153
SN - 0022-328X
VL - 538
SP - 203
EP - 209
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1-2
ER -