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Relevant academic research and scientific papers

Unexpected reactions of anionic intermediates [(μ-RE)(μ-S=CS)Fe2(CO)6]- with so2Cl2. Synthesis and characterization of novel dithioformato-bridged double clusters [(μ-RE)Fe2(CO)6]2(μ-S=CS-μ) (E = S, Se)

The dithioformato-bridged anionic salts [Et3NH][(μ-RE)(μ-S=CS)Fe2(CO)6], generated from CO-bridged anionic complexes [Et3NH][μ-RE)(μ-CO)Fe2(CO)6] and carbon disulfide, reacted in situ with SC2Cl2 in THF to afford a series of novel dithioformato-bridged double clusters [(μ-RE)Fe2(CO)6]2(μ-S=CS-μ) (3a-e) (3a, RE = EtS; 3b, n-PrS; 3c, t-BuS; 3d, PhSe; 3e, p-MeCe6H4Se). A single-crystal diffraction analysis of 3c was undertaken and has confirmed the proposed structure.

Synthesis of single and double butterfly iron carbonyl complexes by reactions of [(μ-RSe)(μ-CO)Fe2(CO)6]- anions. Crystal structures of (μ-p-MeC6H4Se)[μ-PhCH2N(H)C=S]Fe 2(CO)6 and [(μ-PhSe)(μ-MeAs)Fe2(CO)6]2

The in situ reactions of the [Et3NH]+ and [MgBr]+ salts of [(μ-RSe)(μ-CO)Fe2(CO)6]- (1) anions with PhC(Cl)=NPh gave single butterfly complexes (μ-RSe)(μ-PhC=NPh)Fe2(CO)6 (2, R=Ph; 3, R=p-MeC6H4; 4, R=Et), whereas those of the [Et3NH]+ salts of 1 with R′N=C=S afforded single butterfly complexes (μ-RSe)[μ-R′N(H)C=S]Fe2(CO)6 (5, R=Ph, R′=Ph; 6, R=p-MeC6H4 R′=Ph; 7, R=p-MeC6H4, R′=PhCO; 8, R=p-MeC6H4, R′=PhCH2). Compound 8 could also be prepared by reaction of the [MgBr]+ salt of 1 (R=p-MeC6H4) with PhCH2NCS followed by treatment with CF3CO2H. More interestingly, while the [Et3NH]+ salt of 1 (R=Ph) reacted with Et3OBF4 to give a carbyne ligand-bridged single butterfly complex (μ-PhSe)(μ-EtOC)Fe2(CO)6 (9), reaction of the [Et3NH]+ salt of 1 (R=Ph) with MeAsI2 produced a MeAs-AsMe ligand-bridged double butterfly complex [(μ-PhSe)(μ-MeAs)Fe2(CO)6]2 (10). All the new complexes, 2-10, were characterized by elemental analysis and various spectroscopic methods, for complexes 8 and 10, the structures were also confirmed by X-ray diffraction techniques.

Synthesis of double and quadruple butterfly Fe/E cluster complexes via a new type of selenium-centered anions (μ-RE). See abstract

The [Et3NH]+ or [MgBr]+ salts of anions [(μ-RE)(μ-CO)Fe2(CO)6]- (1, E = S, Se, Te) reacted with (μ-Se2)Fe2(CO)6 followed by treatment of the [Et3NH]+ or [MgBr]+ salts of the intermediate selenium-centered anions (μ-RE)(μ-Se-)[Fe2(CO)6]2 (μ4-Se) (3) with monohalide PhCH2Br or MeI to give a series of double butterfly Fe/E cluster complexes (μ-RE)(μ-R1Se)-[Fe2(CO)6]2 (μ4-Se) (4, RE = EtS, R1 = PhCH2; 5, t-BuS, PhCH2; 6, p-MeC6H4Se, PhCH2; 7 p-MeC6H4Se, Me; 8, p-MeC6H4Te, PhCH2; 9, p-MeC6H4Te, Me). Similarly, reaction of the in situ prepared [Et3NH]+ salt of the intermediate selenium-centered anion (μ-t-BuS)(μ-Se-)-[Fe2(CO)6]2 (μ4-Se) with dihalide 1,2-(BrCH2)2C6H4 or 1,3-(BrCH2)2-5-MeC6H3 afforded quadruple butterfly Fe/E cluster {(μ-t-BuS){Fe2(CO)6]2 (μ4-Se)}2 (μ-1-SeCH2C6H4CH2Se-2-μ (10) or double butterfly Fe/E cluster (μ-t-BuS)[(μ-1-SeCH2-3-BrCH2-5-MeC6H 3)[Fe2(CO)6]2 (μ4-Se) (11) and quadruple butterfly Fe/E cluster {(μ-t-BuS)[Fe2(CO)6]2 (μ4-Se)}2(μ-1-SeCH2-5- MeC6H3CH2Se-3μ) (12), respectively. All the new products 4-11 have been characterized by elemental analysis, IR 1H and 77Se NMR spectroscopy, and for 4, 7, and 9 single-crystal X-ray diffraction techniques.

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

The reactions of cationic carbyne complexes of manganese and rhenium, [η-C5H5(CO)2M≡CC6 H5]BBr4 (1, M = Mn; 2, M = Re), with diiron anionic compounds [Et3NH][Fe2(μ-CO) (μ-SeR)(CO)6] (3, R = C6H5; 4, R = p-CH3C6H4) in THF at low temperature gave the dimetal bridging carbene complexes [MFe{μ-C(SeR)C6H5} (CO)5(η-C5H5)] (10, M = Mn, R = C6H5); 11, M = Mn, R = p-CH3C6H4; 13, M = Re, R = C6H5; 14, M = Re, R = (p-CH3C6H4), [η-C5H5M(CO)3] (7, M = Mn; 12, M = Re), and [Fe2(μ-SeR)2(CO)6] (8, R = C6H5; 9, R = p-CH3C6H4). Complexes 1 and 2 also react with [MgBr][Fe2(μ-CO) (μ-SeC2H5)(CO)6] (5) to produce [Fe2(μ-SeC2H5)2(CO)6] (15) and dimetal bridging carbene complexes [MnFe{μ-C(SeC2H5)C6H5} (CO)5(η-C5H5)] (17) and [ReFe{μ-C(SeC2H5)C6H5} (CO)5(η-C5H5)] (18), respectively. 2 reacts similarly with [MgBr][Fe2(μ-CO)(μ-SeC4H9-n) (CO)6] (6) to give [Fe2(μ-SeC4H9-n)2(CO)6 ] (16) and a Re-Fe bridging carbene complex [ReFe{μ-C(SeC4H9-n)C6H5}(CO) 5(η-C5H5)] (19), while the analogous reaction of 1 with 6 produced an unexpected trimetal bridging carbyne complex [MnFe2(μ-H)(μ-CO)2(μ3 -CC6H5(CO)6) (η-C5H5)] (20). The structures of complexes 9, 10, 13, 18, and 20 have been established by X-ray diffraction studies.

Synthesis of doubly-bridged Fe/Se and Fe/Te complexes via reactions of the [MgX]+ salts of anions [(μ-RE)(μ-CO)Fe2(CO)6]- (E=Se,Te).: Crystal structure of (μ-p-MeC6H4Te)(μ-PhC=NPh)Fe2(CO) 6

The reactions of Grignard reagents RMgX with elemental Se or Te in THF, followed by treatment of the intermediates RSeMgX or RTeMgX with Fe3(CO)12 at room temperature (r.t.), were found to give [MgX]+ salts of anions [(μ-RSe)(μ-CO)Fe2(CO)6]- (2) and [(μ-RTe)(μ-CO)Fe2(CO)6]- (3), respectively. Furthermore, the [MgX]+ salts of anions 2 (R=Et) reacted in situ with the electrophile Ph2AsCl to afford (μ-EtSe)(μ-Ph2As)Fe2(CO)6 (4), whereas the [MgX]+ salts (R=p-MeC6H4) reacted with the electrophile PhNCS, followed by treatment with another electrophile MeI to give (μ-p-MeC6H4Se)(μ-PhN(Me)C=S)Fe2(CO) 6 (5). Similarly, the [MgX]+ salts of anions 3 (R=Et, t-Bu, i-Bu) were found to react sequentially with the electrophiles PhCCPh and CF3COOH to yield (μ-RTe)(μ-σ,π-PhC=CHPh)Fe2(CO)6 (6a, R=Et; 6b, R=t-Bu; 6c, R=i-Bu), whereas reactions of the [MgX]+ salts of anions 3 (R=Et, Ph, p-MeC6H4) with the electrophiles Ph2AsCl or PhC(Cl)NPh produced (μ-RTe)(μ-Ph2As)Fe2(CO)6 (7a, R=Et; 7b, R=p-MeC6H4) and (μ-RTe)(μ-PhC=NPh)Fe2(CO)6 (8a, R=a(axial)-Ph; 8b, R=e(equatorial)-Ph; 9a, R=a-p-MeC6H4; 9b, R=e-p-MeC6H4), respectively. The reaction courses for the formation of Fe/Se and Fe/Te complexes 4-9 were discussed briefly and the structures of these new complexes, along with two other new Fe/Te complexes (μ-RTe)2Fe2(CO)6 (R=Et, i-Bu), were characterized by elemental analysis and spectroscopy, as well as for complex 9b, whose structure was confirmed further by X-ray diffraction analysis.

Formation of (μμ-RE)(μ-S-)Fe2(CO)6 and (μ-RE)(μ-Se-)Fe2(CO)6 (E = S, Se) anions and a comparative study of their reactions with SO2Cl2, ClC(O)ZC(O)Cl (Z = (CH2)2, C6H4), or P-MeC6H4SO2Cl.

The CO-bridged anions [(μ-RE)(μ-CO)Fe2(CO)6]- reacted with S8 to form the sulfur-centered anions (μ-RE)(μ-S-)Fe2(CO)6 (4; E = S, Se), whereas reaction of the anions with Se8 yielded the selenium-centered anions (μ-RE)(μ-Se-)Fe2(CO)6 (6; E = S, Se). Interestingly, reaction of 4 with SO2Cl2 afforded the S - S-bonded clusters [(μ-RE)Fe2(CO)6]2(μ-S-S) (5), whereas reaction of 6 with SO2Cl2 produced the μ4-Se clusters [(μ-RE)Fe2(CO)6]2(μ4-Se) (8); clusters 8 could also be produced by the action of anions 6 on succinoyl chloride or p-phthaloyl chloride, while the μ4-8 clusters [(μ-RE)Fe2(CO6]2(μ4-S) (9) were generated by reaction of anions 4 with the above organic bis acid chlorides under similar conditions. Also, reaction of 4 (E = S) with p-MeC6H4SO2Cl gave the μ4-S clusters [(μ-RE)Fe2(CO)6]2(μ4-S) (9; E = S) and the expected Fe2S2 butterfly clusters (μ-RE)(μ-p-MeC6H4SO2S)Fe 2(CO)6 (10), whereas anion 6 reacted with p-MeC6H4SO2Cl to afford the unexpected S=O-bridged complexes (μ-RE)(μ-p-MeC6H4SO2)Fe 2(CO)6 (11) and μ4-Se clusters 8. Clusters 11 could be also prepared through direct reaction of the precursor of 6, i.e. [(μ-RE)(μ-CO)Fe2(CO)6]-, with p-MeC6H4SO2Cl. For some of these reactions the mechanisms were preliminarily proposed. The structures of 15 new cluster compounds have been characterized by C/H analysis and IR, 1H NMR, and MS spectroscopy; those of [(μ-EtS)Fe2(CO)6]2(μ4-Se) (8a) and (μ-EtS)(μ-p-MeC6H4SO2)Fe 2(CO)6 (11a) have been confirmed by X-ray diffraction analyses.

Reactions of [Et3NH][(μ-RE)(μ-CO)Fe2(CO)6] (E = S, Se) salts with sulfur(I) chloride and with carbon disulfide. Crystal structure of the (μ-PhSe) (μ-PhCH2SC=S)Fe2(CO)6 complex

The salts of [Et3NH][(μ-RE)(μ-CO)Fe2(CO)6] (1) react with S2Cl2 to give double-cluster complexes [(μ-RE)Fe2(CO)6]2(μ-S-S-μ) (2a-f) (2a, RE = EtS; 2b, PhS; 2c, n-BuS; 2d, t-BuS; 2e, PhSe; 2f, p-CH3C6H4Se), whereas the salt of [Et3NH][(μ-PhSe)(μ-CO)Fe2(CO)6] reacts with CS2 followed by treatment with diverse organic halides to afford single-cluster complexes (μ-PhSe)(μ-ZSC=S)Fe2(CO)6 (3a-c) (3a, Z = PhCH2; 3b, PhCOCH2; 3c, EtO2CCH2), double-cluster complexes [(μ-PhSe)Fe2(CO)6]2(1,3-(μ-S=C-SCH 2)2C6H4] (3d) and [(μ-PhSe)Fe2(CO)6]2-[1,4-(μ-S=C-SCH 2)2C6H4] (3e), and triple-cluster complex [(μ-PhSe)Fe2(CO)6]3[1,3,5-(μ-S=C-SCH 2)3C6H3] (3f). The crystal structure of 3a was determined by X-ray diffraction techniques.