10.1021/ic990870l.s001
Douglas B. Grotjahn
Douglas B.
Grotjahn
H. Christine Lo
H. Christine
Lo
Jason Dinoso
Jason
Dinoso
Charles D. Adkins
Charles D.
Adkins
Chunbang Li
Chunbang
Li
Steven P. Nolan
Steven P.
Nolan
John L. Hubbard
John L.
Hubbard
Studies of the Synthesis and Thermochemistry of Coordinatively Unsaturated Chelate
Complexes (η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)IrL<sub>2</sub> (L<sub>2</sub> = TsNCH<sub>2</sub>CH<sub>2</sub>NTs, TsNCH<sub>2</sub>CO<sub>2</sub>, CO<sub>2</sub>CO<sub>2</sub>)
American Chemical Society
2000
ligand
C 2 O 4
CH 3 CN
TsNCH 2 CO 2
TsNCH 2 CH 2 NTs
Ir
C 5
CO 2 CO 2
2000-05-20 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Studies_of_the_Synthesis_and_Thermochemistry_of_Coordinatively_Unsaturated_Chelate_Complexes_sup_5_sup_-C_sub_5_sub_Me_sub_5_sub_IrL_sub_2_sub_L_sub_2_sub_TsNCH_sub_2_sub_CH_sub_2_sub_NTs_TsNCH_sub_2_sub_CO_sub_2_sub_CO_sub_2_sub_CO_sub_2_sub_/3626136
A comparative synthetic, structural, and thermochemical study on a series of chelate complexes containing the
fragment (η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ir [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ir(TsNCH<sub>2</sub>CH<sub>2</sub>NTs) (<b>1</b>), (η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ir(TsNCH<sub>2</sub>CO<sub>2</sub>) (<b>2</b>), (η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ir(CO<sub>2</sub>CO<sub>2</sub>) (<b>3</b>)] was performed to clarify the roles of carboxylato and sulfonamido ligands. Whereas <b>1</b> and <b>2</b> are
monomeric in solution and in the solid state, <b>3</b> appears to exist as an oligomer or polymer, (<b>3</b>)<i><sub>n</sub></i>, which can be
broken up by addition of a ligand L such as a phosphine, CO, or 2-methoxypyridine to form (η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ir(L)(CO<sub>2</sub>CO<sub>2</sub>) (<b>6</b>). The synthesis of (<b>3</b>)<i><sub>n</sub></i> from [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)IrCl(μ-Cl)]<sub>2</sub> required the use of silver oxalate in CH<sub>3</sub>CN, but if
other solvents were used, the bridging oxalato complex (η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)IrCl(μ-η<sup>2</sup>-η<sup>2</sup>-C<sub>2</sub>O<sub>4</sub>)ClIr(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>) (<b>7</b>) was
obtained and identified by X-ray diffraction. Enthalpies for reaction of THF-soluble monomers <b>1</b> and <b>2</b> with
PMe<sub>3</sub> were determined to be −28.7(0.5) and −28.5(0.4) kcal mol<sup>-1</sup>, respectively. The oligomerization behavior
of <b>3</b> may be a result of reduced σ- or π-donation of carboxylato ligands compared to <i>N</i>-tosylamido ligands,
because the values for ν<sub>CO</sub> in oxalato and bissulfonamido complexes <b>6</b>−CO and (η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ir(CO)(TsNCH<sub>2</sub>CH<sub>2</sub>NTs) (<b>4</b>−CO) were 2064 and 2042 cm<sup>-1</sup>, respectively.