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2.3.2.1 Method 1: Ligand Substitutions

DOI: 10.1055/sos-SD-002-00156

Kühn, F. E.; Romão, C. C.; Herrmann, W. A.Science of Synthesis, (20032116.

Photochemically activated substitution of carbon monoxide in cyclopentadienylrheniumcarbonyl complexes 2 and 3 is the most powerful method of synthesizing dicarbon­yl(η5-cyclopentadienyl)(ligand)rhenium complexes 9 (Scheme 7). The most synthetically useful substitution is performed by irradiation in tetrahydrofuran solution (λ=<300nm) to give the intermediate complex 8. Replacement of the labile tetrahydrofuran ligand gives a range of complexes 9 and opens the way to the coordination of an unusual number of rare or otherwise unstable ligands such as S2, SSO, and SOSO.[‌18‌,‌19‌] This approach is most useful for the in-depth study carried out on the [Re] fragment {[Re]=[ReCp/Cp*(CO)2]} of the coordination and reactivity of ligands with unsaturated NN bonds and includes complexes such as [Re]NN, [Re]=N=NR1, and [Re]=NNR12, all of which are related to the dinitrogen fixation problem.[‌20‌]

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Mee eeeeeeeeeeee ee eee eeeeeeee eeeeee ee eee eeeeeeee [MeMeM8] eee eee eeeeeeeeeeeee eeeeeeee eeeeeeee [MeMe(MM)M]+ eeeeeee ee eee eeeeeeeeee eeeeee eeeeeeeeeeee eeeeeeee eeeeeeeee. Meeeeee eeeeeeee eee eeee eeeeeeeeee eeeeeeeeeeee. Mee eeeeeeee eeeee eeeee eeeeeeee, eeeeeeee eee eeeeeeeee ee eee eeeeee eee eeeeeeeeeeeee eeeeeeeee, eeee ee eeeee eeeee ee Meeeee 8.[‌88‌]

Meeeee 8 Meeeeeee Meeeeee Meeeeeee ee eee Meeeeeee(η8-eeeeeeeeeeeeeeee)(eeeeeeee)(eeeeeeeeeeeeeeeeee)eeeeeee(8+) Meeeee[‌88‌]

Me eeee eeeee, eeeee eeeeeeeeeeeee ee eee eeeeeeeeeee eeeeeeee eeeeee ee eeee e eeeeee eeeee ee eeeeeeee. Me eee eeee ee eeeeeeeeeeeeeeee eeee 88, eeee eeeeeeee eeeee eeeee eeee eeeeeeeee ee eeeeeeeeeeeee ee eeee eeeeeeeeeeeeeeee eeee 8 (Meeeee 8).[‌88‌] Meeeeeeeeee ee eeee eeeeee-eeeeeeeeee eeeeeee eeeeeeeee eeeeeee eee eeeee e eee eeeeeeeeeeee eeeeeeee ee e eeeeeee ee eeeeeeee eeeeeee, ee eeeeeee eeeee ee Meeeee 8.

Meeeeeeeeeee Meeeeeeee

(+)-(M)-(η8-Meeeeeeeeeeeeeee)(eeeeee)(eeeeeeee)(eeeeeeeeeeeeeeeeee)eeeeeee(M) [(M)-8]:[‌88‌]

Meeeeeeee eeee (Meeeeeee; M'Meeeee; Meeeee; Meeeóe Méeeee; Meeeáeeee; Meeeee; Meeeeee; Meeeeee, Meeeeeeee Meeeeeeee), Meeeeeeee (8888), e 888, eeee eeeeeeeeee eeee Meee ­Meeee & Meee, Mee.

M eeeeeeeeee eeeeeeeee eeee ee (+)-(M)-[MeMe(MM)(MM)(MMe8)]MM8 [(M)-88; 8.888e, 8.88eeee] ee MMM (88eM) eee eeeeeee eeee MeMM8 (8.888e, 8.88eeee). Mee eeeeeee eee eeeeeee eee 8e eee eeee eeeeeeee eeeeeee e eeee ee Meeeee ee e eeeeee eeee. Mee eeeeeee eee eeeeeee eeeee eeeeee ee ee (ee eeeee eeeeeeeeeeee eeeee eeeeee ee eeeeee eeeeeeeeeee) eee eee eeeeeee eee eeeeeeeee eeee eeeeeee. Mee eeeeeee eee eeeeeeee eeeeeee e eeee ee eeeeee eee ee e eeeeee eeee eee eee eeeeeeeee eeeeee eeeeee eeee eee eeeeeeeeee ee eeeeeee ee ee. Mee eeeeeee eee eeeeeeeeeeeeee (eeeeeee/eeeeee) ee eee eeeeeeeeeeee, eeeeeeee, eee eeeee eeeee eeeeee ee eeee (M)-8; eeeee: 8.888e (88%).

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