Remarkable Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with Diiron Anions [Fe₂(μ-CO)(μ-SeR)(CO)₆]^-. A Route to RSe-Bridged Dimetal Bridging Carbene Complexes

Abstract

The reactions of cationic carbyne complexes of manganese and rhenium, [η-C 5 H 5 (CO) 2 Mt CC 6 H 5 ]BBr 4 (1, M ) Mn; 2, M ) Re), with diiron anionic compoundsComplexes 1 and 2 also react with [MgBr][Fe 2 (µ-CO)(µ-SeC 2 H 5 )(CO) 6 ] (5) to produce [Fe 2 -(µ-SeC 2 H 5 ) 2 (CO) 6 ] (15) and dimetal bridging carbene complexes [MnFe{µ-C(SeC 2 H 5 )C 6 H 5 }-(CO) 5 (η-C 5 H 5 )] ( 17) and [ReFe{µ-C(SeC 2 H 5 )C 6 H 5 }(CO) 5 (η-C 5 H 5 )] ( 18), respectively. 2 reacts similarly with 16) and a Re-Fe bridging carbene complex [ReFe{µ-C(SeC 4 H 9 -n)C 6 H 5 }(CO) 5 (η-C 5 H 5 )] ( 19), while the analogous reaction of 1 with 6 produced an unexpected trimetal bridging carbyne complex [MnFe 2 (µ-H)(µ-CO) 2 (µ 3 -CC 6 H 5 )CO) 6 (η-C 5 H 5 )] (20). The structures of complexes 9, 10, 13, 18, and 20 have been established by X-ray diffraction studies.

Novel Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with Polymetal Carbonyl Anions. An Approach to Trimetal Bridging Carbyne Complexes

“…Compound 7 is a 48-CVE (cluster valence electron) complex, where the Mn and Ru atoms formally have 19 and 17 electrons, respectively, which probably accounts for the presence of the semibridging carbonyl and bridging hydrogen. Several di- and polynuclear ruthenium complexes with semibridging carbonyl and bridging hydrogen ligands have been reported. − The analogous 48-valence- electron structure was found in the complexes [MW 2 (μ 3 -C 2 R 2 )(CO) 7 (η-C 5 H 5 )] (M = Ru, Os), [ReFeCo(μ 3 -CC 6 H 5 )(CO) 8 (η-C 5 H 5 )],7d and [MnFe 2 (μ-H)(μ-CO) 2 (μ 3 -CC 6 H 5 )(CO) 6 (η-C 5 H 5 )] …”

“…The Ru−Ru bond length of 2.860(2) Å in 7 is somewhat longer than that found in the triruthenium bridging carbyne complex [Ru 3 (μ-CNMe 2 )(μ-H)(CO) 10 ] (average 2.818 Å) . The μ-C(6)−Mn, μ-C(6)−Ru(1), and μ-C(6)−Ru(2) distances are 1.99(1), 2.07(2), and 2.08(1) Å, respectively, of which the μ-C(6)−Mn bond distance is closely related to that found in the complexes [MnFeCo(μ 3 -CC 6 H 5 )(μ-CO)(CO) 7 (η-C 5 H 5 )] (1.94(1) Å) 7d and [MnFe 2 (μ-H)(μ-CO) 2 (μ 3 -CC 6 H 5 )(CO) 6 (η-C 5 H 5 )] (2.00(1) Å), and the two μ-C(6)−Ru bond lengths are essentially the same.

2 Molecular structure of 9 , showing the atom-numbering scheme.

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“…Like the trimetal carbonyl anions 3 and 4 , the tetrametal carbonyl anionic compound [(PPh 3 ) 2 N] 2 [Fe 4 (CO) 13 ] ( 5 ) can also react with cationic carbyne complexes 1 and 2 under the same conditions to afford the analogous trimetal bridging carbyne complexes [MnFe 2 (μ-H)(μ-CO) 2 (μ 3 -CC 6 H 5 )(CO) 6 (η-C 5 H 5 )] ( 12 ) and [ReFe 2 (μ-H)(μ-CO) 2 (μ 3 -CC 6 H 5 )CO) 6 (η-C 5 H 5 )] ( 13 ) (eq 4) in high yields (>85%), respectively, among which product 12 is a known compound obtained from the reaction of 1 with reactive [Fe 2 (μ-CO)(μ-SeC 4 H 9 - n )(CO) 6 ] - anion and has been characterized by X-ray crystallography …”

“…The purple-red band was eluted and collected. The solvent was removed under vacuum, and the residue was recrystallized from petroleum ether/CH 2 Cl 2 (10:1) at −80 °C to give 0.33 g (85%, based on 1 ) of 12 as deep purple-red crystals: mp 106 °C dec; IR (CH 2 Cl 2 ) ν(CO) 2077 (s), 2048 (vs), 2014 (s), 1989 (s), 1868 (s, br), 1831 (w) cm -1 ; 1 H NMR (CD 3 COCD 3 ) δ 8.01 (m, 2H, C 6 H 5 ), 7.55 (m, 2H, C 6 H 5 ), 7.33 (m, 1H, C 6 H 5 ), 4.80 (s, 5H, C 5 H 5 ), −23.80 (s, 1H, μ-H); MS m / e 546 (M + ), 518 [M + − CO], 490 [M + − 2CO], 462 [M + − 3CO], 434 [M + − 4CO], 406 [M + − 5CO], 378 [M + − 6CO], 350 [M + − 7CO], 322 [M + − 8CO]. 266 [M + − Fe 2 (CO) 6 ].…”

Synthesis of selenium bridged metallacycles via oxidative addition of diaryl diselenide across Re–Re bond: Novel one-pot reaction approach

“…Petillon and co-workers have reported the dinuclear molybdenum complex [Cp* 2 Mo 2 (CO) 4 (m-SePh) 2 ] from [Cp* 2 Mo 2 (CO) 4 ] and benzene selenol [32]. Reaction of [h-C 5 H 5 (CO) 2 6 ] yielded FeeFe bridged dinuclear complex [Fe 2 (m-SeC 6 H 5 ) 2 (CO) 6 ] [33]. Cyclopentadienyl chromium chalcogenide complex [CpCr(SePh)] 2 Se was obtained from the reaction of [CpCr(CO) 3 ] 2 with Ph 2 Se 2 [34].…”