Bartik, Tamás Weng, Weiqing Ramsden, James A. Szafert, Slawomir Falloon, Stephen B. Arif, Atta M. Gladysz, J. A. New Forms of Coordinated Carbon:  Wirelike Cumulenic C<sub>3</sub> and C<sub>5</sub> sp Carbon Chains that Span Two Different Transition Metals and Mediate Charge Transfer Reactions of (η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Re(NO)(PPh<sub>3</sub>)(C⋮CLi) with W(CO)<sub>6</sub>, Fe(CO)<sub>5</sub>, or Mn(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<i><sub>n</sub></i>Cl<i><sub>5-n</sub></i>), followed by Me<sub>3</sub>O<sup>+</sup> BF<sub>4</sub><sup>-</sup>, give the heterobimetallic C<sub>3</sub>OMe complexes (η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Re(NO)(PPh<sub>3</sub>)(C⋮CC(OMe))M(CO)<i><sub>x</sub></i>(η<sup>5</sup>-C<sub>5</sub>H<i><sub>n</sub></i>Cl<i><sub>5-n</sub></i>)<i><sub>y</sub></i> (M/<i>x</i>/<i>y</i>/<i>n</i> = <b>3</b>, W/5/0/−; <b>4</b>, Fe/4/0/−; <b>5</b>, Mn/2/1/5; <b>6</b>, Mn/2/1/4; <b>7</b>, Mn/2/1/0). Spectroscopic and crystallographic (<b>3</b>) data indicate contributions by <sup>+</sup>ReCCC(OMe)−M<sup>-</sup> resonance forms. Reactions of <b>4</b>−<b>7</b> and BF<sub>3</sub> gas give the title compounds [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Re(NO)(PPh<sub>3</sub>)(CCC)M(CO)<i><sub>x</sub></i>(η<sup>5</sup>-C<sub>5</sub>H<i><sub>n</sub></i>Cl<i><sub>5-n</sub></i>)<i><sub>y</sub></i> (M/<i>x</i>/<i>y</i>/<i>n</i> = <b>9</b>, Mn/2/1/5; <b>10</b>, Mn/2/1/4; <b>11</b>, Mn/2/1/0; <b>12</b>, Fe/4/0/−). Spectroscopic and crystallographic (<b>9</b>) data indicate dominant contributions by fully cumulated <sup>+</sup>ReCCCMn resonance forms. Reactions of (η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Re(NO)(PPh<sub>3</sub>)(C⋮CC⋮CLi) with Mn(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>Cl<sub>5</sub>), Mn(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>Br<sub>5</sub>), or Fe(CO)<sub>5</sub>, followed by Me<sub>3</sub>O<sup>+</sup> BF<sub>4</sub><sup>-</sup>, give the C<sub>5</sub>OMe complexes (η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Re(NO)(PPh<sub>3</sub>)(C⋮CC⋮CC(OMe))M(CO)<i><sub>x</sub></i>(η<sup>5</sup>-C<sub>5</sub>X<sub>5</sub>)<i><sub>y</sub></i> (M/<i>x</i>/<i>y</i>/X = <b>16</b>, Mn/2/1/Cl; <b>19</b>, Mn/2/1/Br; <b>20</b>, Fe/4/0/−). However, Mn(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>) does not react. Reaction of <b>16</b> and BF<sub>3</sub> gives the C<sub>5</sub> complex [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Re(NO)(PPh<sub>3</sub>)(CCCCC)Mn(CO)<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>Cl<sub>5</sub>)]<sup>+</sup> BF<sub>4</sub><sup>-</sup> (<b>21</b>) as a light-sensitive deep brown powder of >94% purity. IR and NMR data show a dominant <sup>+</sup>ReCCCCCMn resonance form. UV−visible spectra of <b>9</b><b>−</b><b>11 </b>and <b>21</b> show intense absorptions at 392, 396, 414, and 480 nm (ε 55 800, 50 900, 49 100, 60 500 M<sup>-1</sup> cm<sup>-1</sup>), respectively, and weaker longer wavelength bands. These are believed to have appreciable rhenium-to-manganese charge-transfer character. CCC;CCCCC;BF 4;C 5 X 5;Cl;C 5 H 5;Mn;BF 3 gas;UV;Different Transition Metals;Mediate Charge Transfer Reactions;Fe;3 O;C 5;C 5 sp Carbon Chains;IR;NMR data show 1998-10-16
    https://acs.figshare.com/articles/journal_contribution/New_Forms_of_Coordinated_Carbon_Wirelike_Cumulenic_C_sub_3_sub_and_C_sub_5_sub_sp_Carbon_Chains_that_Span_Two_Different_Transition_Metals_and_Mediate_Charge_Transfer/3671352
10.1021/ja981927q.s001