%0 Generic
%A Jin, Song
%A Venkataraman, D.
%A DiSalvo, Francis J.
%D 2000
%T Ligand Substitution Reactions of W6S8L6 with Tricyclohexylphosphine (L =
4-tert-Butylpyridine or n-Butylamine): 31P NMR and Structural Studies of
W6S8(PCy3)n(4-tert-butylpyridine)6-n (0 < n ≤ 6) Complexes
%U https://acs.figshare.com/articles/dataset/Ligand_Substitution_Reactions_of_W_sub_6_sub_S_sub_8_sub_L_sub_6_sub_with_Tricyclohexylphosphine_L_4-_i_tert_i_-Butylpyridine_or_i_n_i_-Butylamine_sup_31_sup_P_NMR_and_Structural_Studies_of_W_sub_6_sub_S_sub_8_sub_PCy_sub_3_sub_i_sub_n_sub_i_4-_i_tert_i_-/3627378
%R 10.1021/ic991426l.s001
%2 https://acs.figshare.com/ndownloader/files/5716128
%K n complexes
%K THF
%K tert
%K PR
%K butylpyridine
%K W 6 S 8
%K W 6 S 8 L 6
%K octahedral metal clusters
%K 31 P NMR spectra
%K PCy 3
%K Ligand Substitution Reactions
%K 1 H NMR spectra
%X The substitution reactions by bulky tricyclohexylphosphine (PCy3) ligands on W6S8L6 (L = 4-tert-butylpyridine
or n-butylamine) clusters were investigated to prepare clusters with mixed axial ligands for low-dimensional
cluster linking. When 4−6 equiv of PCy3 are used to react with W6S8(4-tert-butylpyridine)6 (4) in THF, cis-W6S8(PCy3)4(4-tert-butylpyridine)2 (1) is preferentially formed. But when starting with W6S8(n-butylamine)6 (2),
only W6S8(PCy3)6 (3) is produced with 6 equiv of PCy3. Other conditions with fewer equivalents of PCy3 led to
mixtures of partially substituted complexes in the W6S8L6-n(PCy3)n (0 ≤ n ≤ 6, L = 4-tert-butylpyridine or
n-butylamine) series. A significantly distorted structure for 1 helps to explain its preferential formation. 1H NMR
spectra were collected for clusters 1 and 2 and 31P NMR spectra for 1 and W6S8(4-tert-butylpyridine)6-n(PCy3)n
complexes. P−P coupling through P−W−W−P is reported for the first time in octahedral metal clusters and
shown to be very useful in identifying nearly all the W6S8L6-n(PR3)n complexes and their stereoisomers in the
mixtures even before individual species are isolated.
%I ACS Publications