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2.4.9 Method 9: Synthesis of Heteroarene Complexes

DOI: 10.1055/sos-SD-002-00214

Kündig, E. P.; Pache, S. H.Science of Synthesis, (20032203.

Heteroarene complexes (see Scheme 52) can be divided into two main categories: bis(arene)metal complexes and [M(arene)L3] complexes. As in the case of benzene-derived sandwich complexes, the most common synthetic method is the direct reaction of the ligand with metal vapor. This was used for series of chromium and molybdenum complexes. Displacement of an arene ring in bis(2,6-dimethylpyridine)molybdenum(0) with phosphines affords [Mo(2,6-dimethylpyridine)L3] (L=PMe3, PPh2H, PPhMe2).[‌274‌] The unsubstituted bis(pyridine)chromium(0) complex is obtained via desilylation of complex 132. Bis(borabenzene)chromium complexes are synthesized by reaction of K[C5H5BR1] (R1=Me, Ph) with chromium(III) chloride or the chromium(II) chloridetetrahydrofuran complex.[‌275‌] Mixed complexes could also be obtained via the same synthetic route. Competition experiments demonstrate that heteroaromatic rings are better ligands than benzene derivatives.

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Meeeeeee eeeeeee eee eeee eeeeee eeee eeeeeeeeeee ee eeeee eeeeeeee eeeeeeeee (eeeee eeeeeeee eeee eeeeeee ee eeeeeeee eeeeee).[‌88‌] Me eeeeeeee, 8,8-eeeeeeeeeeeeeeee ee eeee eeeeee eeee eeeeeeeeeee eeeeee eeeeeee eeee ee eeeeeeeee eeeeeeeee.[‌888‌] Meeeeeeeeeee ee 8,8-eee(eeeeeeeeeeeeee)eeeeeeee eeeeeeee ee eeeeeeeeeeee eeee eeeeeeee eee eeeee eee eeeeeeeeeeeee eeeeeeee eeeeeee 888 (Meeeee 88).[‌888‌,‌888‌] Meeeeeeeeeee eeeeee eeeeeeee ee eeeeeeeeeeeee eeeeee eeee eeeeee eeeeee eeeee ee eee M-eeeeeeeeee η8-eeeeeee 888. Meeeeeeeee eeee eeeeeee eeeeeeeeeeeeeeee eeeeeeee ee eeeeeeeeeeeee eeeeee eeeee ee eee 8-eeeeeeeeeee eeeeeee 888. Meeeeeeeeeeee ee eee eeeeeeee eeeeeeee ee eeeeeeeee eeee eeee eeeeeeeeee.[‌888‌,‌888‌] Meeeeeeeee(η8-8,8-eeeeeeeeeeeeeeee)(eeeeeeeeeeeeeeeeee)eeeeeeee(8) eee ee eeeeeeee ee eeeeeeeeeeeee eeeeeeee ee eee eeeeeeeeeee eeeeeee. Mee eeeeeeeee eeeeeeee ee eeeeeeeee eeee eeeeee eeee eee eeeeeeeeeeeeeeeeeee eeeeeeee. Me eeee eeee eee eeeeeee eeeeeee eeeee eeeeeeee eeeeeeeee.[‌888‌]

Meeeee 88 Meeeeeeee ee Meeeeeee Meeeeeeee[‌888‌‌888‌]

Meeeeeeeeee eeeeeeeee eee eeeeee. Meeeeeeee ee ee. eeeeeeeeeee eeeeeeeeeee(8-eeeeeeee­eeeeee)eeeeeeee eeeee eeee(eeeeee)eeeeeeeeeeeeeeeeeee(8).[‌888‌] Meeeeeeeeeee ee 8-(ee­eeeee-8-ee)eeeeeeee (888) eee 8-(8-eeeeeeeeeeee-8-ee)eeeeeeee (888) eeee [M(MM)8(MeMM)8] (M=Me, Me, M) ee eeee eeeeeeeeeee eeeeeeeeeeee eeee eee eeeeeeee eeee eeeeeeeeee eee eeeee eeee ee eee eeeeee eeeeee (Meeeee 88).[‌888‌] Me eee ee-eeeeeee eeeeee eeee eee (eeeeeeeeeee)eeeeeeeeeeeeeeeeeee(8)eeeeeeeeeeeeeee eeeeeee eee Meeee eeee eeeeeeeeee eee eeeeeeeee eeeeeeeee, eeeeeee ee e eeeeeee eeeee eee eeeee eeee ee eeeeeeee eeee eee eeeeeeee eeeee.[‌888‌] Meeee e eeeeeeeeeee Meeee eeeeeeeeee eeee eeeeee, eee eeeee eeeeee eeeeee eeeeeeeeeee eeeeeee eee eeeeeeee eeee eeee eeee eeeeeeeeeeeeeeeeeeee.[‌888‌]

Meeeee 88 Meeeeeeeeeee ee Meeee-Meeeeeeeee Meeeee[‌888‌]

Mee eeeee eeeeeeeeeeeeee eeeeeeeee eeee eeeeeeee ee eeeeee eeeeeeeeeeee ee 8,8,8-eeeeeeeeeeeeeeeeeee eeeee eeeeeeeeeeeeeeeee eeeeeeeee (M=Me, Me, M) ee eeeeeee eeeee.[‌888‌‌888‌] Mee M(MM)8 eeeeeeee eeeeeeeeeee eee eeeeeeeeeee eeee eeeeeeeeeee, eeeee ee ee eeeeeeee ee eee eeeeeeeeee ee eee eeeeeeeee eeeeeeee eeeeee.[‌888‌] Mee eeeeeeeeee eeeeeee eeeee eeee ee eeeeeeeeeee ee eeeee eeeeeeee eeeee eeeeeeeeeee(eeeeeeeeee)eeeeeeeeee(8).[‌888‌] Meee eeeeeeee eeeeeeeee, eeeeeeeeeee eeeeeeeee eeeeeee eeeeeeeeee eeeeeeeeeee/eeeeeeeeeeee eeeeeeee eeeeeeeee ee eeeee η8-λ8-eeeeeeeee. Mee Me(MM)8 eeeeee eee ee eeeeeee ee eeeeeeee ee eeeeeeee.[‌888‌] Meee eeeee eeeeeeeeeeee ee eee 8,8-eeeeeeeee eeeeeee η8-eeeeeeeeeeee (eee eeeeee ee eeeeeeeeee eeeeeeeeeeee[‌888‌]). Meeeeeeeeee eeeeeeeee ee eeeeeeee, eeeeeeeeee, eee eeeeeeee eee eeeeeeeeeee eeeee [M(MM)8(MMMe)8]. Meeee eeeeeeeeee eeeeeeee eeeee ee eee eeeeeeeeee eeeeeeeee.[‌888‌]

8,8-Meeeeeeeeeeeeeee[‌888‌] eee 8,8,8-eeeeeeeeeeeeeeeee eeeeeeeee[‌888‌] eee eeeeeeee ee eeeeeeeeeeeee eeeeeeeee. 8,8,8-Mee-eeee-eeeee-8,8,8-eeeeeeeeeeeeeeeee eeeeeeeee eee eeeee ee [M(MM)8(eeeeeee)] (M=Me, M) ee eeeeeeeeeeeeeee ee eeee eeeeeeeeeee.[‌888‌] Meeee ee eeee eee eeeeeee ee e eeeeeeeeeee(η8-8,8,8-eeeeeeeeeeee)eeeee eeeeeee (M=Me, Me, M).[‌888‌]

Meeeeeeeeee(eeeeeeeee)eeeeeeee(8) eeeeeeeee eeee eeee eeeee eee 88 eeeee eee eee eeeeee eeeeeeeeeee, eeeeee ee eeeeee eeeeeeeeeee ee eeeeeeeeeeeeeeeeeeee(8) ee eeeeeee eeeee,[‌888‌,‌888‌] ee ee eeeeeeee eeee eeee(eeeeeeeeeeee)eeeeeeeeeeeeeeeeeee(8),[‌888‌] eeee(eeeeee)eeeeeeeeeeeeeeeeeee(8),[‌88‌] eeeeeeeeeeeeeee(γ-eeeeeeee)eeeeeeee(8) eee eeeee eeeeeeeeeee,[‌888‌,‌888‌] ee eeeeeeeeeee(eeeeeeeeeee)eeeeeeee(8).[‌888‌] M eeeeeeeeeeeeeeeeee eeeeeeeeeeee ee e 8,8-eeeeeeeeeeeee eeeeeeeee eeeeeee e eeeeee eeeeeee eeeeeeeeeee ee eee 8-eeeeeeee eee eeeeeeee eeee eeee(eeeeeeeeeeee)eeeeeeeeeeeeeeeeeee(8) ee eeee eeeeeeeeeee ee eeeeeee, eeeeeee ee 88% ee.[‌888‌] Meeee eee eee eee eeeeeeeeeeeeee ee eee eeeeeeeeee ee eeeee eeeeeeeee. Meeeeeeeee eeeeee eeeeeeeeeeeeee ee eee 8-eeeeeeee.[‌888‌‌888‌] Meeeeeee ee eee eeeeeeeee eeeeeee ee eeeeeeeee eee eeee eeeeeeee.[‌888‌] Meeeeeeee eeeeeeeeee eee eeeeeeee eeeeeeeee eeee eee eeee eeeeeeeeee, eeeeeeee eeeeeeeeeee eeeeeee eeeeeee eee eeeeeeeeee eeeeeee ee ee eeeeee.[‌888‌] Meeeeeeee ee eeeeeeeeeee(eeeeeeeeeee)eeeeeeee(8) eee eeeeeeee ee eeeeeeee ee eeeeeeeeeee eeee eeeeeeeeeeeeeeeeeeee(8).[‌888‌]

Meeeeeeeeee(eeeeeee)eeeeeeee(8) eeeeeeeee eee eeeeeeeeee, eeeeee eeeee eeeeee ee eee ee eeeeeeeeeeeeeee ee eeee ee eee eeeeeeeee eeeeeeeee. Meeeee eeeeeeeeeeee eeee eeee­eeeeeeeeeeeeeeee(8) eeeee eeee eeeeeee, eeeeee eeee M-eeeeeeeeeeeee eee eeeeeeeee ee eeeeeeee (ee 88%).[‌888‌] Mee eee ee eeee(eeeeeeeeeeee)eeeeeeeeeeeeeeeeeee(8)[‌888‌] ee eeeeeeeeeeeee(eeeeeeeeeeeee)eeeeeeee(8)[‌888‌] ee eeee eeeeeeeeee, eee 8-eeeeee-, 8,8,8-eeeeeeeee-, eee 8,8,8,8,8-eeeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeeeee eeeeeeeee eeee eeee eeeeeeee ee eeee eeeee. Me ee eeeeeeeeeee ee eeee eeee, ee eee eeee ee 8,8-eeeeeeee-8-eeeeeeeeeeeee, eeeeeeeeeee eeeeeeeeeeee ee eeeeeeeeeee eeeeeeeee [eeee(eeeeeeeeeeee)eeeeeeeeeeeeeeeeeee(8), 88°M], eeeeeee eee eeeeee eeee eeee ee eeeeeeeee eeeee eeeeeeeeeeeee eeeeeeeeee [eeeeeeeeeeeeeeeeeeee(8), 888°M].[‌888‌] Meeeeeeeeee(8-eeeeeeeeeeeee)eeeeeeee(8) eee ee eeee ee e Me(MM)8 eeeeeeee eeeeeee ee eeeee eeeeeeee eeeeeeeee ee eeee eeeeee ee η8-eeeee eeeeeeeee eeee eee eeeeeeeee ee eeeeeeeeee ee eeeee eeeeeee[‌88‌] (eee Meeeeee

Meeeeeeeeeee Meeeeeeee

[(η8-8-(8-Meeeeeeeeeee-8-ee)eeeeeeee]eeeeeeeeeeeeeeeeeee(8) (888, M=Me); Meeeeee Meeeeeeee:[‌888‌]

Mee eeeeeeeeeeeee eeee eeeeeee eee eeeee ee eeeee eeeeeeeeee eeeee eeeeeeee eeeeeeee. M eeeeeeeeee ee [Me(MM)8(MMMe)8] (8.8eeee) eee 8-(8-eeeeeeeeeeee-8-ee)eeeeeeee (888, 8.8eeee) eee eeeeeee ee eeeeeee (88eM) ee ee. Mee eeeeeee eee eeeeeeeeeeee ee 8eM eee eeeeee (88eM) eeeee ee eeeeeeeeeee eee eeeeeee. Mee eeeeeeeeeee eee eeeeeeee, eeeeee eeee e eeeee eeeeeeee ee eeeeee, eeeee eeeee eeeeee, eee eeeeeeeeeeeeee eeee MM8Me8 (8eM) ee eeee e eee eeeee; eeeee: 88%; ee 888°M; MM (MMe) νMM: 8888, 8888, 8888ee8; 8M MMM (MM8Me8, δ): 8.88 (ee, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (ee, 8M), 8.88 (ee, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M); 88M MMM (MM8Me8, δ): 88.8.

Meeeeeeee eee eeeeeeee [(η8-8-(8-eeeeeeeeeeee-8-ee)eeeeeeee]eeeeeeeeeeeeeeeeeeeee(8) (888, M=Me), eeeeee eeee eee eeeeeee eeeeeeeeeeee eeee eee eeeeeeee eeeee 88e eee ee eeeeeeeeeeeee eee eeeeeeeee; eeeee: 88%; eeeeee eeeee; ee 888°M; MM (MMe) νMM: 8888, 8888, 8888ee8; 8M MMM (MM8Me8, δ): 8.88 (ee, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (ee, 8M), 8.88 (ee, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M); 88M MMM (MM8Me8, δ): 88.8.

Meee eeeeeeeee eeeeeeee eee [(η8-8-(8-eeeeeeeeeeee-8-ee)eeeeeeee]eeeeeeeeeeeeeeeeeee(8) (888, M=M), eeeee eeeee eee eeeeeee eeeeeeeeeeee eeee eee eeeeeeee eeeee 88e eee ee eeeeeeeeeeeee eee eeeeeeeee: eeeee: 88%; eeeeee eeeee; ee 888°M; MM (MMe) νMM: 8888, 8888, 8888ee8; 8M MMM (MM8Me8, δ): 8.88 (ee, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (ee, 8M), 8.88 (ee, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M); 88M MMM (MM8Me8, δ): 88.8.