Jiabi Chen

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)CS]Fe2(CO)6 and [(μ-PhSe)(μ-MeAs)Fe2(CO)6]2

Abstract 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.

Reaction of tricarbonyl(exo-cyclopentadienyl-η5-cyclohexadienyl)manganese with aryllithium reagents: crystal structures of [C5H5-{(η5-C6H6)(CO)2Mn=C(OC2H5)C6H5}] and [C5H5-{(η5-C6H6)(CO)2Mn=C(OC2H5)C6H4CH3-o}]

Abstract The reaction of tricarbonyl(exo-cyclopentadienyl-η5-cyclohexadienyl)manganese (1) with aryllithium reagents, ArLi (Ar=C6H5, o-, m-, p-CH3C6H4, p-CH3OC6H4, p-CF3C6H4), in ether at low temperature afforded acylmetalate intermediates, followed by alkylation with Et3OBF4 in an aqueous solution at 0°C to give the six alkoxycarbene manganese complexes [C5H5-{(η5-C6H6)(CO)2Mn=C(O-C2H5)Ar}] ( 2 , Ar = C 6 H 5 ; 3 , Ar = o- CH 3 C 6 H 4 ; 4 , Ar =m- CH 3 C 6 H 4 ; 5 , Ar = p- CH 3 C 6 H 4 ; 6 , Ar = p- CH 3 OC 6 H 4 ; 7 , Ar = p- CF 3 C 6 H 4 ) . The molecular structures of 2 and 3 have been established by X-ray diffraction studies.

Reactions of di-μ-carbonyl-cis-μ-(1-5-η:1′-5′-η-dicyclopentadienyl-dimethylsilane)bis(carbonyliron) with aryllithium reagents. Crystal structures of [Fe2(μ-CO){μ-C(OC2H5)C6H5}(CO)2{(η5-C5H4)2Si(CH3)2}] and [Fe2(μ-CO){μ-C(OC2H5)C6H4OCH3-p}(CO)2{(η5-C5H4)2Si(CH3)2}]

Abstract The reactions of di-μ-carbonyl-cis-μ-(1-5-η:1′-5′-η-dicyclopentadienyl-dimethyl silane)bis(carbonyliron), [Fe2(μ-CO)2(CO)2{(η5-C5H4)2Si(CH3)2}] (1), with aryllithium reagents, ArLi (Ar=C6H5, o-, m-, p-CH3C6H4, p-CH3OC6H4, p-ClC6H4, p-CF3C6H4), in ether at low temperature afforded acylmetalate intermediates, followed by alkylation with Et3OBF4 in aqueous solution at 0°C or in CH2Cl2 at −30°C gave the (dicyclopentadienyldimethylsilane)diiron bridging alkoxycarbene complexes [Fe2(μ-CO){μ-C(OC2H5)Ar}(CO)2{(η5-C5H4)2Si(CH3)2}] (2, Ar=C6H5; 3, Ar=o-CH3C6H4; 4, Ar=m-CH3C6H4; 5, Ar=p-CH3C6H4; 6, Ar=p-CH3OC6H4; 7, Ar=p-ClC6H4; 8, Ar=p-CF3C6H4), among which the structures of 2 and 6 have been established by X-ray diffraction studies.

Unexpected reactions of (cyclooctatetraene) diiron hexacarbonyl with aryllithium reagents: Crystal structures of [(CO)3Fe(1–4-η:5–7-ηC8H9)(CO)2Fe (COC6H5)] and [(CO)3Fe(1–4-η:5–8-η-C8 H8)(CO)2FeC(OC2H5)C6H5]

Abstract The reaction of (cyclooctatetraene)diiron hexacarbonyl (1) with aryllithium reagents ArLi (Ar = C6H5, o-, m-, p-CH3C6H4, p-CH3OC6H4 in ether at low temperature afforded acylmetalate intermediates. Subsequent alkylation with Et3OBF4 in aqueous solution at 0°C gave the (8,8-dihydro-1-4-η:5-7-η-cyclooctatrienyl) tricarbonylirondicarbonyl(arylformacyl)iron complexes [(CO)3Fe(1–4-η:5–7-η-C8H9) (CO)2Fe(COAr)] (2a-e) (2a, Ar = C6H5; 2b, Ar = o-CH3C6H4; 2c, Ar = m-CH3C6H4; 2d, Ar = p-CH3C6H4; 2e, Ar = p-CH3OC6H4) and (1–4-η:5–8-η-cyclooctatetraene)tricarbonylirondicarbonyl [ethoxy(aryl)carbene]iron complexes [(CO)3Fe(1–4-η:5–8-η-C8H8) (CO)2FeC(OC2H5)Ar] (3a-e) (3a, Ar = C6H5; 3b, Ar = o-CH3C6H4; 3c, Ar = m-CH3C6H4; 3d, Ar = p-CH3C6H4; 3e, Ar = p-CH3OC6H4). The structures of 2a and 3a have been established by X-ray diffraction studies, which indicate that the Fe(CO)3 unit and the (CO)2Fe(COC6H5 moiety in 2a and the (CO)2FeC(OC2H5)C6H5 moiety in 3a are on opposite sides of the cyclooctatetraene ring.

Unusual reactions of [{μ-(phthalazine-N2:N3)}Fe2(μ-CO)(CO)6] with organolithium reagents. A novel coordination mode of 1,2-diazane diiron carbonyl compounds

[{μ-(Phthalazine-N2:N3)}Fe2(μ-CO)(CO)6] (1) reacts with organolithium reagents, RLi (R = CH3, C6H5, p-CH3C6H4, p-CH3OC6H4, p-CF3C6H4, p-C6H5C6H4), followed by treatment with Me3SiCl to give the novel diiron carbonyl complexes with a saturated N–N six-membered diazane ring ligand, [{C6H4CH(R)NNCH2}Fe2(CO)(CO)6] (2, R = CH3; 3, R = C6H5; 4, R = p-CH3C6H4; 5, R = p-CH3OC6H4; 6, R = p-CF3C6H4; 7, R = p-C6H5C6H4). Compounds 4 and 5 were treated with [(NH4)2Ce(NO3)6] to afford the aryl-substituted phthalazine-coordinated diiron carbonyl compounds [(μ-{1-(p-CH3C6H4)-phthalazine-N2:N3})Fe2(μ-CO)(CO)6] (8) and [(μ-{1-(p-CH3OC6H4)-phthalazine-N2:N3})Fe2(μ-CO)(CO)6] (9), respectively. The structures of complexes 4 and 9 have been established by X-ray diffraction studies.

Studies on olefin-coordinating transition metal carbene complexes: XIX . Synthesis and structural characterization of the cycloalkene ligated carbonyl-chromium and -tungsten carbene complexes

Abstract Reaction of norbornadiene(tetracarbonyl)-chromium (1) and -tungsten (2) with aryllithium reagents, ArLi (Ar  C6H5, o-,m-,p-CH3C6H4, p-CH3OC6H4, p-CF3C6H4), in ether at low temperature, and subsequent alkylation of the acylmetalate intermediates formed with Et3OBF4 in aqueous solution at 0°C gave seven crystalline complexes with the compositions C7H8(CO)3CrC(OC2H5)Ar (4–9) and C7H8(CO)3WC(OC2H5)Ar (10) formulated as norbornadiene(tricarbonyl)[ethoxy(aryl)carbene]-chromium and -tungsten complexes, respectively. Complex 7 has been characterized by X-ray diffraction. Complex 7 is orthorhombic, space group P212121 with a = 10.372(3), b = 12.093(6), c = 14.154(9) A, V = 1775.27 A3, and Z = 4, final R = 0.0529 and Rw = 0.0562 for 1385 observed reflections. The 1,5-cyclooctadiene(tetracarbonyl)tungsten compound (3) reacts similarly to give analogous carbene complexes C8H12(CO)3WC(OC2H5)Ar (11–13).

Unusual reactions of cationic bridging carbyne complexes of dimethylsilane-bridged bis(η5-cyclopentadienyl)diiron tricarbonyl with carbonylmetal anions

The reactions of he dimethylsilane-bridged cationic carbyne complexes of diiron, [Fe^2(μ-Car)(CO)^2 [η~5-C^5H^4Si(CH^3)^2}BBr^4(1,Ar=C^6H^5; 2, Ar=Pcf^3H^4), with carbonylmetal anionic compounds Na[M(CO)^5CN](4,M=Cr;5, M=Mo; 6, M=W) in THF at low temperature afford diiron bridging carbene complexes [Fe^2(μ-(CO)){μ-C(Ar)NCM(CO)^5}(CO)^2{(η~5-C^5H^4)^2Si(CH^3)^2}](9, M=Cr, Ar=C^6H^5; 10, M =Mo, Ar=C^6H^5; ; 11, M=W,Ar=C^6H^5; 12, M=Cr, Ar=p-CF^3C^6H^4; 13, M=Mo, Ar=p-CF^3C^6H^4; 14, M=W, Ar=p-CF^3C^6H^4). In contrast to the reaction of 1 and 2 cationic carbyne complex [Fe^2(μ-CO)(μ-CC^6H4CH^3-p)(CO)^2{(η~5-C^5H^4)^2Si(CH^3)^2}]BBr^4(3) reacts with 4-6 under the same conditions to produce novel cationic bridging carbyne complexes [Fe^2(μ-CO)(μ-CC^6H4CH^3-p)(CO)^2{(η~5-C^5H^4)^2Si(CH^3)^2}]+[M(CO)^5CN]-(15,M=CR; 16,M=MO; 17,M=W). Analogous cationic bridging carbyne complex [[Fe^2(μ-CO)(μ-CC^6H4CH^3-p)(CO)^2{(η~5-C^5H^4)^2Si(CH^3)^2}+[Fe(CO)^4CN]-(18) can also be obtained from the reaction of 3 with Na[Fe(CO)^4CN] (7). Complex 15 or 16 reacts with NaSR (R=CH^3, C^6H^5, p-CH^3C^6H^4) to give bridging mercaptocarbene complexes [Fe^2(μ-CO){μ-C(SR)C^6H^4CH^3-p} (CO)^2{η~5-C^5H^4)^2Si(CH^3)^3}] (19, R=CH^3; 20, R=C^6H^5; 21, R=p-CH^3C^6H^4) in high yields. The related reaction of 1 with NaN(SiMe^3)^2 affords a novel benzonitrile-coordinated diiron complex [[Fe^2(μ-CO^2(CO)NCC^6H^5{η~5-C^5H^4)^2Si(CH^3)^2}] (22). Unexpectedly, the reactions of 1 and 2 with 7 yield diiron bridging arylcarbene comlexes [Fe^2(μ-CO){μC(H)Ar}(CO)^2{(η~5-C^5H^4)^2Si(CH^3)^2}](23, Ar=C^6H^5; 24, Ar=p-CF^3C^6^H^4). The products 23 and 24 and bridging p-tolyl-carbene complex [Fe^2(μ-CO){μ-(CO){μ-C(H)C^6H^4CH^3-p}(CO)^2{η~5-C^5H^4)^2Si(CH^3)^2}] (2) were also obtained from the reactions of 1-3 with [PPh^3)^2N][Cr(CO)^4NO] (8). The structures of 14.15,22, and 23 have been established by X-ray crystallography.

Novel dimetal bridging carbene complexes derived from a terminal carbonyl dimetal compound. Syntheses, structures and reactivities of 7H-indene-coordinated diiron bridging carbene complexes

Pentacarbonyl-7H-indenediiron, [Fe2(CO)5(eta3,eta5-C9H8)] (1), reacts with aryllithium, ArLi (Ar = C6H5, p-C6H5C6H4), followed by alkylation with Et3OBF4 to give novel 7H-indene-coordinated diiron bridging alkoxycarbene complexes [Fe2{mu-C(OC2H5)Ar}(CO)4(eta4,eta4-C9H8)] (2, Ar = C6H5; 3, Ar = p-C6H5C6H4). Complexes 2 and 3 react with HBF4.Et2O at low temperature to yield cationic bridging carbyne complexes [Fe2(mu-CAr)(CO)4(eta4,eta4-C9H8)]BF4 (4, Ar = C6H5; 5, Ar = p-C6H5C6H4). Cationic 4 and 5 react with NaBH4 in THF at low temperature to afford diiron bridging arylcarbene complexes [Fe2{mu-C(H)Ar}(CO)4(eta4,eta4-C9H8)] (6, Ar = C6H5; 7, Ar = p-C6H5C6H4). The similar reactions of 4 and 5 with NaSC6H4CH3-p produce the bridging arylthiocarbene complexes [Fe2{mu-C(Ar)SC6H4CH3-p}(CO)4(eta4,eta4-C9H8)] (8, Ar = C6H5; 9, Ar = p-C6H5C6H4). Cationic 4 and 5 can also react with anionic carbonylmetal compounds Na[M(CO)5(CN)] (M = Cr, Mo, W) to give the diiron bridging aryl(pentacarbonylcyanometal)carbene complexes [Fe2{mu-C(Ar)NCM(CO)5}(CO)4(eta4,eta4-C9H8)] (10, Ar = C6H5, M = Cr; 11, Ar = p-C6H5C6H4, M = Cr; 12, Ar = C6H5, M = Mo; 13, Ar = p-C6H5C6H4, M = Mo; 14, Ar = C6H5, M = W; 15, Ar = p-C6H5C6H4, M = W). Interestingly, in CH2Cl2 solution at room temperature complexes 10-15 were transformed into the isomerized 7H-indene-coordinated monoiron complexes [Fe(CO)2(eta5-C9H8)C(Ar)NCM(CO)5] (16, Ar = C6H5, M = Cr; 17, Ar = p-C6H5C6H4, M = Cr; 18, Ar = C6H5, M = Mo; 19, Ar = p-C6H5C6H4, M = Mo; 20, Ar = C6H5, M = W; 21, Ar = p-C6H5C6H4, M = W), while complex 3 was converted into a novel ring addition product [Fe2{C(OC2H5)C6H4C6H5-p-(eta2,eta5-C9H8)}(CO)5] (22) under the same conditions. The structures of complexes 2, 6, 8, 14, 18 and 22 have been established by X-ray diffraction studies.

Synthesis, structure and reactivity of novel pyridazine -coordinated diiron bridging carbene complexes

[{mu-(Pyridazine-N(1):N(2))}Fe(2)(mu-CO)(CO)(6)](1) reacts with aryllithium reagents, ArLi (Ar = C(6)H(5), m-CH(3)C(6)H(4)) followed by treatment with Me(3)SiCl to give the novel pyridazine-coordinated diiron bridging siloxycarbene complexes [(C(4)H(4)N(2))Fe(2){mu-C(OSiMe(3))Ar}(CO)(6)](2, Ar = C(6)H(5); 3, Ar =m-CH(3)C(6)H(4)). Complex 2 reacts with HBF(4).Et(2)O at low temperature to yield a cationic bridging carbyne complex [(C(4)H(4)N(2))Fe(2)(mu-CC(6)H(5))(CO)(6)]BF(4)(4). Cationic 4 reacts with NaBH(4) in THF at low temperature to afford the diiron bridging arylcarbene complex [(C(4)H(4)N(2))Fe(2){mu-C(H)C(6)H(5)}(CO)(6)](5). Unexpectedly, the reaction of 4 with NaSCH(3) under similar conditions gave the bridging arylcarbene complex 5 and a carbonyl-coordinated diiron bridging carbene complex [Fe(2){mu-C(SCH(3))C(6)H(5)}(CO)(7)](6), while the reaction of NaSC(6)H(4)CH(3)-p with 4 affords the expected bridging arylthiocarbene complex [(C(4)H(4)N(2))Fe(2){mu-C(SC(6)H(4)CH(3)-p)C(6)H(5)}(CO)(6)](7), which can be converted into a novel diiron bridging carbyne complex with a thiolato-bridged ligand, [Fe(2)(mu-CC(6)H(5))(mu-SC(6)H(4)CH(3)-p)(CO)(6)](8). Cationic can also react with the carbonylmetal anionic compound Na(2)[Fe(CO)(4)] to yield complex 5, while the reactions of 4 with carbonylmetal anionic compounds Na[M(CO)(5)(CN)](M = Cr, Mo, W) produce the diiron bridging aryl(pentacarbonylcyanometal)carbene complexes [(C(4)H(4)N(2))Fe(2)-{mu-C(C(6)H(5))NCM(CO)(5)}(CO)(6)](9, M = Cr; 10, M = Mo; 11, M = W). The structures of complexes 2, 5, 6, 8, and 9 have been established by X-ray diffraction studies.

Reactions of[Mn(CO)3{η5-C5H4[(η5-C6H6)Mn(CO)3]}] and[WMe(CO)3{η5-C5H4[(η5-C6H6)Mn(CO)3]}]with aryllithium reagents

The reactions of [Mn(CO) 3 {η 5 -C 5 H 4 [( η 5 -C 6 H 6 )Mn(CO) 3 ]}] 1 and [WMe(CO) 3 {η 5 -C 5 H 4 [( η 5 -C 6 H 6 )Mn(CO) 3 ]}] 2 with aryllithium reagents, LiR (R = o-, m-, p-MeC 6 H 4 , Ph, p-MeOC 6 H 4 or p-CF 3 C 6 H 4 ), in diethyl ether at low temperature afforded acylmetalate intermediates, which on alkylation with Et 3 OBF 4 in aqueous solution at 0 °C gave alkoxycarbene complexes [Mn(CO) 3 {η 5 -C 5 H 4 [( η 5 -C 6 H 6 )(OC) 2 Mn C(OEt)R]}] and [WMe(CO) 3 {η 5 -C 5 H 4 [( η 5 -C 6 H 6 )(OC) 2 Mn C(OEt)R]}]. The structure of [Mn(CO) 3 {η 5 -C 5 H 4 [( η 5 -C 6 H 6 )(OC) 2 Mn C(OEt)C 6 H 4 Me-o]}], established by X-ray diffraction, shows that the carbene ligand is attached to the manganese atom co-ordinated to the η 5 -cyclohexadienyl moiety.