Synthesis of an Se-Bridged Triiron Acyl Cluster Complex and the Fischer-Type Carbene Complex Derived from It:  Isolation of Rotational Isomers

Shieh, Minghuey; Chen, Horng-Sun; Chi, Hsin-Hung; Ueng, Chuen‐Her

doi:10.1021/ic000301+

Cited by 19 publications

(3 citation statements)

References 39 publications

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“…The π-allyl complexes are well-known; however, those containing α-allylcarbonyl ligands are rare. ,,, To the best of our knowledge, this type of μ 3 -η 1 :η 1 :η 3 -allylcarbonyl bonding mode is unprecedented before our study . In 1 , the bond distances of C−C bonds in the allyl ligand are 1.403(8) and 1.428(8) Å, indicative of the double-bond character, and are close to those (1.401(9) and 1.419(8) Å) in the related selenium complex [Et 4 N][(μ 3 -Se)Fe 3 (CO) 9 (μ 3 -η 1 :η 1 :η 3 -C(O)C(H)CCH 2 )] . Complex 2 shows the continuous conjugated double-bonding character in the O−C carbene , C carbene -Fe, and C carbene −allyl bonds.…”

Section: Resultsmentioning

confidence: 55%

“…Cluster 2 is isolated in the trans form in the solid state, and the cis product is not obtained under our conditions, due to the greater stability of the trans form (Chart ). This is in contrast to the related Se system, where the cis and trans forms are both isolable at room temperature due to greater rotational energy . The INSIGHT II calculation showed that the total energy of cluster 2 (trans form) is 153.52 kcal/mol and that of the cis form is 157.32 kcal/mol, explaining the quick isomerization of these two forms in solution at room temperature and the successful isolation of cluster 2 in the trans form in the solid state at low temperature.…”

Section: Discussionmentioning

confidence: 75%

“…Vahremkamp et al reported a series of heteronuclear metal complexes starting from the mononuclear acetylide complexes LnMC⋮CR, and Wojcicki et al have studied metal clusters containing C 3 fragments by use of the mononuclear propargyl complexes LnMCH 2 C⋮CR or the allenyl complexes LnMCHC CCRR‘ with other transition-metal carbonyls. , Some polynuclear carbonyl clusters with simple alkynes have also been studied . Nevertheless, reports of the incorporation of main-group-element-bridged transition- metal carbonyl clusters with unsaturated hydrocarbon fragments are scarce. − Recently, we reported the first isolation of two rotational isomers of a Fischer-type carbene cluster which was afforded from the reaction of [SeFe 3 (CO) 9 ] 2- with the bifunctional propargyl bromide followed by careful methylation . This successful isolation was thought to be attributable to the existence of a continuous unsaturated conjugation system due to the introduction of the propargyl fragment.…”

Section: Introductionmentioning

confidence: 99%

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Reaction of the Tellurium-Capped Triiron Cluster [TeFe₃(CO)₉]²^-with the Bifunctional Propargyl Bromide: Formation of a Series of Novel Organic Te−Fe−CO Complexes

Shieh¹,

Chen

Lai

2004

Organometallics

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When [TeFe 3 (CO) 9 ] 2was treated with 1 equiv of propargyl bromide in MeCN, the novel acyl complex [Et 4 N][(µ 3 -Te)Fe 3 (CO) 9 (µ 3 -η 1 :η 1 :η 3 Cluster 1 can be viewed to consist of a TeFe 3 core which is linked by the novel allylcarbonyl ligand C(O)CHCCH 2 in a µ 3 -η 1 :η 1 :η 3 fashion. Further oxidation of cluster 1 occurs via organo ligand loss and bond rearrangement to give the oxidation product Te 2 Fe 3 (CO) 9 . In addition, when cluster 1 was methylated with CF 3 SO 3 Me, the Fischer-type carbene complex (µ 3 -Te)-Fe 3 (CO) 9 (µ 3 -η 1 :η 1 :η 3 -C(OMe)C(H)CCH 2 ) (2) was afforded. When the ratio of reactants and reaction solvent was varied, the detailed reaction of [TeFe 3 (CO) 9 ] 2with propargyl bromide could be further investigated. When [TeFe 3 (CO) 9 ] 2was treated with excess propargyl bromide in MeCN, the two new butterfly clusters Te 2 Fe 2 (CO) 6 (CHdCdCH 2 ) 2 (3) and Te 2 Fe 2 (CO) 6 (CH 2 CtCH)(CHdCdCH 2 ) (4) were obtained along with cluster 1. While cluster 3 displays a Te 2 Fe 2 metal core with two allenyl ligands attached to the tellurium atoms in anti positions, cluster 4 consists of a Te 2 Fe 2 core with each tellurium atom coordinated to one allenyl or one propargyl ligand in an anti position. Further investigation of [TeFe 3 (CO) 9 ] 2with propargyl bromide in a molar ratio of 1:2 or 1:4 in CH 2 Cl 2 showed that the oxidation product (µ 3 -Te)Fe 3 (CO) 9 (µ 3 -η 1 :η 2 :η 1 -C(Me)dCH) (5) was afforded, in addition to the formation of 1, 3, and 4. Cluster 5 can be viewed to be composed of a TeFe 3 core coordinated with the propyne ligand C(Me)tCH, which acts as a 4e donor. This paper describes the detailed reactions of [TeFe 3 (CO) 9 ] 2with the bifunctional propargyl bromide in terms of the reaction solvents, the ratio of the reactants, and the chalcogen effect, and the reactivities and structural features of the resultant clusters with the novel organo moieties are systematically compared and discussed.

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Section: Resultsmentioning

confidence: 55%

Section: Discussionmentioning

confidence: 75%

Section: Introductionmentioning

confidence: 99%

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Reaction of the Tellurium-Capped Triiron Cluster [TeFe₃(CO)₉]²^-with the Bifunctional Propargyl Bromide: Formation of a Series of Novel Organic Te−Fe−CO Complexes

Shieh¹,

Chen

Lai

2004

Organometallics

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Copper Halide‐Bridged Ruthenium Telluride Carbonyl Complexes: Discovery of the Semiconducting Cluster Chain Polymer {[PPh₄]₂[Te₂Ru₄(CO)₁₀Cu₄Br₂Cl₂]⋅THF}_∞

Shieh

Hsu

Sheu

et al. 2007

Chemistry A European J

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A new series of Te-Ru-Cu carbonyl complexes was prepared by the reaction of K(2)TeO(3) with [Ru(3)(CO)(12)] in MeOH followed by treatment with PPh(4)X (X=Br, Cl) and [Cu(MeCN)(4)]BF(4) or CuX (X=Br, Cl) in MeCN. When the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was first treated with PPh(4)X followed by the addition of [Cu(MeCN)(4)]BF(4), doubly CuX-bridged Te(2)Ru(4)-based octahedral clusters [PPh(4)](2)[Te(2)Ru(4)(CO)(10)Cu(2)X(2)] (X=Br, [PPh(4)](2)[1]; X=Cl, [PPh(4)](2)[2]) were obtained. When the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was treated with PPh(4)X (X=Br, Cl) followed by the addition of CuX (X=Br, Cl), three different types of CuX-bridged Te-Ru carbonyl clusters were obtained. While the addition of PPh(4)Br or PPh(4)Cl followed by CuBr produced the doubly CuBr-bridged cluster 1, the addition of PPh(4)Cl followed by CuCl led to the formation of the Cu(4)Cl(2)-bridged bis-TeRu(5)-based octahedral cluster compound [PPh(4)](2)[{TeRu(5)(CO)(14)}(2)Cu(4)Cl(2)] ([PPh(4)](2)[3]). On the other hand, when the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was treated with PPh(4)Br followed by the addition of CuCl, the Cu(Br)CuCl-bridged Te(2)Ru(4)-based octahedral cluster chain polymer {[PPh(4)](2)(Te(2)Ru(4)(CO)(10)Cu(4)Br(2)Cl(2)).THF}(infinity) ({[PPh(4)](2)[4].THF}(infinity)) was produced. The chain polymer {[PPh(4)](2)[4].THF}(infinity) is the first ternary Te-Ru-Cu cluster and shows semiconducting behavior with a small energy gap of about 0.37 eV. It can be rationalized as resulting from aggregation of doubly CuX-bridged clusters 1 and 2 with two equivalents of CuCl or CuBr, respectively. The nature of clusters 1-4 and the formation and semiconducting properties of the polymer of 4 were further examined by molecular orbital calculations at the B3LYP level of density functional theory.

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Chalcogen‐Bridging Iron Carbonyl Complexes: Cluster Growth and Reactivity Comparison

Shieh

Lai

2002

J Chinese Chemical Soc

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Quite a num ber of chalcogen-containing iron car bonyl clus ters have been syn the sized and struc tur ally char ac ter ized, and the in ter est ing struc tural trans for ma tions and re ac tiv i ties of these clus ters have been system at i cally in ves ti gated as well. In this short re view, we would like to de scribe the re cent de vel op ments on iron car bonyl in cor po rated chalcogen atom (E = Te, Se, S) clus ters in our lab o ra tory and will fo cus on the system atic syn the sis, re ac tiv ity, and clus ter growth in this ex cit ing sys tem. IN TRO DUC TIONHieber et al. re ported the gen eral syn the sis of main group-iron car bonyl com plexes around the 1950s, 1 in which a wide range of main group ox ides are used to re act with Fe(CO) 5 /KOH in meth a nol so lu tions. The chem is try of main group-transition metal clus ters has grown steadily ever since. Since 1980, the work in this area has been ex ten sively expanded and a large amount of novel bond ing ver sa til ity and re ac tiv ity of the re sul tant clus ters have been re vealed and discussed. 2,3 This re port will mainly em pha size the re cent de velop ments of chalcogen-containing iron car bonyl clus ters in our lab o ra tory, deal ing spe cially with the syn the sis, chem i cal re ac tiv ity com par i son, and clus ter growth pro cesses from smaller clus ters to larger-sized clus ters. As we know, many metal car bonyl clus ters tend to frag ment when ap plied in cat a lytic re ac tions. Com pounds con tain ing bonds be tween tran si tion metal and group 16 ele ments (S, Se, Te) have been stud ied be cause of the po tential use ful ness of these main group el e ments as bridges between dif fer ent metal at oms in clus ters and as sta bi liz ing lig ands to pre vent their frag men ta tion. In con trast to the larger num ber of sul fur con tain ing clus ters, those con taining se le nium and tel lu rium have been much less ex plored. Due to the rel a tively larger ra dius and Lewis acid ity of se lenium and tel lu rium, cer tain ge om e try and re ac tiv ity dif ferences have been sug gested for the re sul tant clus ters. Nev erthe less, re cent stud ies in di cate that elec tronic and steric factors of the lig ands may as well play a cou pling ef fect on the for ma tion of the chalcogen iron car bonyl clus ters, and most of the re sul tant clus ters, seem not reg u larly to fol low the sim ple chem i cal trend. Hence, more work has to be done to at tempt to an swer this so phis ti cated ques tion. We will describe in this re view the chalcogen-containing iron clus ters ba si cally in terms of the ef fects of main group el e ments and the in com ing groups. TEL LU RIUM-CONTAINING IRON CLUS TERS Hieber's Syn the sisIn the 1950s, Hieber et al. re ported that TeO3 2-could react with the ba sic iron car bonyl so lu tions fol lowed by acid i fica tion to af ford Te 2 Fe 2 (CO) 6 (1) 4 and Te 2 Fe 3 (CO) 9 (2). 1c,5Ever since, the re ac tiv ity of 1 and 2 has been ex ten sively stud ied, and they have proved to be very use ful in many cluster build ...

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Synthesis of an Se-Bridged Triiron Acyl Cluster Complex and the Fischer-Type Carbene Complex Derived from It: Isolation of Rotational Isomers

Cited by 19 publications

References 39 publications

Reaction of the Tellurium-Capped Triiron Cluster [TeFe₃(CO)₉]²^-with the Bifunctional Propargyl Bromide: Formation of a Series of Novel Organic Te−Fe−CO Complexes

Reaction of the Tellurium-Capped Triiron Cluster [TeFe₃(CO)₉]²^-with the Bifunctional Propargyl Bromide: Formation of a Series of Novel Organic Te−Fe−CO Complexes

Copper Halide‐Bridged Ruthenium Telluride Carbonyl Complexes: Discovery of the Semiconducting Cluster Chain Polymer {[PPh₄]₂[Te₂Ru₄(CO)₁₀Cu₄Br₂Cl₂]⋅THF}_∞

Chalcogen‐Bridging Iron Carbonyl Complexes: Cluster Growth and Reactivity Comparison

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Synthesis of an Se-Bridged Triiron Acyl Cluster Complex and the Fischer-Type Carbene Complex Derived from It: Isolation of Rotational Isomers

Cited by 19 publications

References 39 publications

Reaction of the Tellurium-Capped Triiron Cluster [TeFe3(CO)9]2-with the Bifunctional Propargyl Bromide: Formation of a Series of Novel Organic Te−Fe−CO Complexes

Reaction of the Tellurium-Capped Triiron Cluster [TeFe3(CO)9]2-with the Bifunctional Propargyl Bromide: Formation of a Series of Novel Organic Te−Fe−CO Complexes

Copper Halide‐Bridged Ruthenium Telluride Carbonyl Complexes: Discovery of the Semiconducting Cluster Chain Polymer {[PPh4]2[Te2Ru4(CO)10Cu4Br2Cl2]⋅THF}∞

Chalcogen‐Bridging Iron Carbonyl Complexes: Cluster Growth and Reactivity Comparison

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Reaction of the Tellurium-Capped Triiron Cluster [TeFe₃(CO)₉]²^-with the Bifunctional Propargyl Bromide: Formation of a Series of Novel Organic Te−Fe−CO Complexes

Reaction of the Tellurium-Capped Triiron Cluster [TeFe₃(CO)₉]²^-with the Bifunctional Propargyl Bromide: Formation of a Series of Novel Organic Te−Fe−CO Complexes

Copper Halide‐Bridged Ruthenium Telluride Carbonyl Complexes: Discovery of the Semiconducting Cluster Chain Polymer {[PPh₄]₂[Te₂Ru₄(CO)₁₀Cu₄Br₂Cl₂]⋅THF}_∞