Experimental
General Data. All reactions except thioether syntheses were conducted under N2 atmospheres. Chemicals were treated as follows: acetone, 2-butanone and CHCl3, distilled from
anhydrous CaSO4; THF, ether, benzene, and toluene, distilled from Na/benzophenone; CH2Cl2 and
C6H5Cl distilled from CaH2 and then P2O5; etc.; ClCH2CH2Cl (99%, Fluka), DMF (99%, Fluka),
methanol and ethanol, used as received; CDCl3, vacuum transferred from CaH2 or P2O5; etc.; nBuLi (Acros, 2.5 or 1.6 M in hexanes), standardized;1 K2PtCl4 (Strem), water-insoluble residue
removed by filtration; Br(CH2)6CH=CH2 (4; 97%, Aldrich or Fluka), etc., used as received.
IR spectra were recorded on Mattson Polaris FT or ASI React-IR 1000 spectrometers. NMR
spectra were obtained on Varian 300 MHz or Jeol 400 MHz spectrometers. Mass spectra were
recorded on Finnigan MAT 95 or Micromass Zabspec high resolution instruments. Microanalyses
were conducted by Atlantic Microlab or with a Carlo Erba EA1110 instrument (in-house). Osmotic
molecular weights were determined by Galbraith.
Compound
formula
e.g.:
(H3C)(Ph3P)(ON)Re(-C5H4(CH2)6CH=CH(CH2)6--
C5H4)Re(NO)(PPh3)(CH3) (Compound number e.g.: 6; usually given by the person writing a
manuscript). A Schlenk flask was charged with (here put SM formula or number if given earlier)
(0.xxx g, 0.xxx mmol), X (0.xxx g, 0.xxx mmol), and CH2Cl2 (XX mL). The solution was refluxed
(1.5 h). Solvent was removed by rotary evaporation. The brown foam was dissolved in a minimum
of CH2Cl2. The solution was rinsed through a Celite/silica plug (1 and 2 cm above a frit). Solvent
was removed by oil pump vacuum to give Y as an orange solid (0.xxx g, 0.xxx mmol, XX%; Z/E
23:7754,55a).
m.p. 72 °C.
Elemental analysis calcd (%) for C62H70N2O2P2Re2 (1309.61): C 56.86, H 5.39. Found: C
56.52, H 5.64.
IR (cm-1, medium): NO = 1621 (s).
UV-vis (concentration): XXX (extinction).
MS (FAB, 3-NBA/CH2Cl2): m/z (%): 1310 (6) [M]+, 1295 (2) [M-CH3]+; no other peaks
above 300 of > 25%.
1
H NMR (300 MHz, CDCl3, 20 °C):  = 7.42-7.35 (m, 30 H, 6Ph), 5.35 (m, 2 H, CH=CH),
5.21, 4.61, 4.56, 4.10 (4 m, 4  2 H, 2C5H4), 2.19 (m, 4 H, 2C5H4CH2), 1.94 (m, 4 H, 2CH2CH=),
1.54-1.21 (m, 16 H, 8CH2), 0.89 (d, 3J(H,P) = 6 Hz, 6 H, 2ReCH3);
13C{1H}
NMR (75 MHz,
CDCl3, 20 °C):  = 136.5 (d, 1J(C,P) = 51 Hz, i-Ph), 133.6 (d, 2J(C,P) = 11 Hz, o-Ph), 130.3 (s,
CH=CH), 129.7 (d, 4J(C,P) = 2 Hz, p-Ph), 128.1 (d, 3J(C,P) = 10 Hz, m-Ph), 112.7 (s, i-C 5H4R),
91.7, 88.7, 86.4, 84.0 (4 s, other C5H4R), 32.6 (s, CH2CH=, E), 30.9 (s, CH2), 29.5 (s, CH2), 29.3 (s,
CH2), 28.9 (s, CH2), 28.0 (s, CH2), -32.9 (d, 2J(C,P) = 7 Hz, ReCH3);
CDCl3, 20 °C):  = 26.0 (s).
-2-
31P{1H}
NMR (121 MHz,