Polynuclear Complexes with Propynylidene C3-Bridges: General Synthetic Route to Bis-, Tris-, and Tetrakis(ethynylcarbene) Complexes

Hartbaum, Cornelia; Roth, Gerhard; Fischer, Helmut

doi:10.1002/(sici)1099-0682(199802)1998:2<191::aid-ejic191>3.3.co;2-k

Cited by 9 publications

(13 citation statements)

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“…This is the first example of a dimercury(II) diacetylide complex to be characterized crystallographically. Reported structures of mononuclear Hg(II) acetylides are also limited . There are no apparent short intermolecular interactions between the fluorenyl rings as well as the Hg(II) centers.…”

Section: Resultsmentioning

confidence: 99%

Binuclear Gold(I) and Mercury(II) Derivatives of Diethynylfluorenes

et al. 2001

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A new series of bis(alkynyl) gold(I) and mercury(II) d10 complexes incorporating fluorenyl-based linking units are reported. The binuclear complexes [LAuC⋮CRC⋮CAuL] and their isoelectronic mercury(II) congeners [R‘HgC⋮CRC⋮CHgR‘] (L = tertiary phosphines; R = fluorene-2,7-diyl, dihexylfluorene-2,7-diyl, 9-((ferrocenylphenylene)methylene)fluorene-2,7-diyl, fluoren-9-one-2,7-diyl, 9-(dicyanomethylene)fluorene-2,7-diyl; R‘ = Me, Ph) were prepared in very good yields by the base-catalyzed dehydrohalogenation reaction of the corresponding metal chloride precursors with the appropriate diethynylfluorene derivatives HC⋮CRC⋮CH at room temperature. All the compounds have been fully characterized by FTIR, NMR and electronic absorption spectroscopies and FAB mass spectrometry. The solid-state molecular structures of [Ph3PAuC⋮CRC⋮CAuPPh3] (R = 9,9-dihexylfluorene-2,7-diyl, fluoren-9-one-2,7-diyl) and [MeHgC⋮CRC⋮CHgMe] (R = fluoren-9-one-2,7-diyl) have been determined crystallographically, the last of which represents the first dimercury diacetylide to be structurally characterized. Absorption studies suggest that it is possible to fine-tune the optical gap of this class of materials by modifying the electronic properties of the substituent at the 9-position of the central fluorene spacer. The solution redox chemistry of these fluorene-linked binuclear complexes as revealed by cyclic voltammetry indicates some degree of electronic communication between the 9-substituent of the fluorenyl ring and the terminal metal groups via the conjugated alkynyl bridge. Most of the complexes in this study have been shown to exhibit rich photophysical behavior, and a discussion on their emission properties in terms of the nature of metal groups and their auxiliary ligands as well as the fluorene spacer was made.

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Section: Resultsmentioning

confidence: 99%

Binuclear Gold(I) and Mercury(II) Derivatives of Diethynylfluorenes

et al. 2001

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“…J. T. Baker, silica for flash chromatography) was argon-saturated. The complexes 1 , , 4a , b , 7a , b , 9 , 11 , 13 , 15 , NEt 4 [(CO) 5 WCPh(OMe)H], and [PdCl 2 (MeCN) 2 ] 23 were prepared according to literature procedures. NMR spectra were determined on Bruker AC 250, Bruker DRX 600, and JEOL JNX 400 instruments; chemical shifts are reported relative to internal TMS ( 1 H and 13 C).…”

Section: Methodsmentioning

confidence: 99%

“…Gladysz et al synthesized several heterobimetallic complexes by reaction of [Cp*(NO)(PPh 3 )Re(C⋮C) x ] - with [Mn(CO) 3 Cp], [Fe(CO) 5 ], [W(CO) 6 ], or [Re 2 (CO) 10 ] and subsequent alkylation of the resulting metalate with [Me 3 O]BF 4 . 2d, Other approaches are the substitution of alkynylcarbene anions for the halide in metal halides and the Pd-catalyzed coupling of C-stannylated carbene complexes with [XML n ]. Recently, we reported the synthesis of a series of heterobinuclear complexes [(CO) 5 MC(NR 2 )(C⋮C) x M‘L‘ n ] (M = Cr, W; NR 2 = NMe 2 , NHMe; x = 1−3; M‘ = Sn, Mn, Re, Fe, Ru, Rh, Ni, Pd) by the latter methods. , “Linear” trinuclear (M‘ = Fe, Ni, Pd, Pt, Hg), , L-shaped (M‘ = Ti) trinuclear, and star-shaped tetra- (M‘ = B, P) 16 and pentanuclear complexes (M‘ = Ge, Sn) 16 were also accessible. Complexes of type F (R = H; x = 1) have also been studied .…”

Section: Introductionmentioning

confidence: 99%

Bimetallic Complexes with Conjugated C₄, C₆, C₁₀, and C₁₄ Bridges: Synthetic Routes to Alkynediyl-Bridged Bis(carbene) Complexes

et al. 1999

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The reaction of [(CO)5WC(Ph)H] with Me2NC⋮CNMe2 affords two complexes: the binuclear complex [(CO)5WC(NMe2)(Me2N)CW(CO)5] (2) and the insertion product [(CO)5WC(NMe2)C(NMe2)C(Ph)H] (3). Sequential reaction of the (dimethylamino)ethynylcarbene complex [(CO)5WC(NMe2)C⋮CH] (4a) with nBuLi, W(CO)6, and F3CSO3Me yields the new ethynediyl-bridged binuclear alkoxycarbene−aminocarbene complex [(CO)5WC(NMe2)C⋮C(MeO)CW(CO)5] (5). Treatment of 4a and of [(CO)5CrC(NMe2)C⋮CH] (4b) with nBuLi and iodine gives the new iodine-substituted complexes [(CO)5MC(NMe2)C⋮CI] (M = W (6a), M = Cr (6b)). By Pd-catalyzed coupling of 6a,b with the C-stannylated ethynylcarbene complexes [(CO)5MC(NMe2)C⋮CSn(nBu)3] (7a,b) the butadiynediyl-bridged bis(carbene) complexes [(CO)5MC(NMe2)(C⋮C)2(Me2N)CM(CO)5] (8a,b) are obtained. Analogously, from [(CO)5WC(NMe2)(C⋮C) x H] (x = 2, 3) and nBuLi/I2 amino(iodobutadiynyl)carbene and amino(iodohexatriynyl)carbene complexes [(CO)5WC(NMe2)(C⋮C) x I] (x = 2 (10), 3 (14)) are obtained. Pd-catalyzed coupling with the corresponding C-stannylated alkynylcarbene complexes finally affords the binuclear C10(NMe2)2- and C14(NMe2)2-bridged complexes [(CO)5WC(NMe2)(C⋮C) x (Me2N)CW(CO)5] (x = 4 (12), 6 (16)). All alkynediyl-bridged bis(carbene) complexes are stable at room temperature. The spectroscopic data of 5 indicate that it is best described as a hybrid of a dipolar allenyl-type compound and an alkynylcarbene complex. In contrast, the C⋮C units in the binuclear complexes 8a,b, 12, and 16 are essentially localized.

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“…Recently synthetic routes to binuclear alkynyl Á/carbene complexes (A) and alkynediyl-bridged biscarbene complexes (B) have been developed [5]. ) by substitution of alkynylcarbene anions for the halide in metal halides [4,5], or c) by Pd-catalyzed coupling of C-stannylated alkynylcarbene complexes with metal halides [5].…”

Section: Introductionmentioning

confidence: 99%

Mono- and binuclear 3-amino cyclobuten-2-one complexes of tungsten—facile migration of pentacarbonylmetal fragments in carbene complexes

Fuss

Weibert

Fischer

2003

Journal of Organometallic Chemistry

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Reaction of [(CO) 5 W Ä/C(NMe 2) Ã/C Å/CH] (1a) with n-BuLi and [M(CO) 6 ] (M0/W, Cr, Mo) in THF and chromatography on silica affords the 3-dimethylamino cyclobuten-2-on-1-ylidene tungsten complex [(CO) 5 W Ä/ / ae C ÃCH ÄC(NMe 2) ÃC /(Ä/O)] (2). Complex 2 is also isolated, after chromatography, from the reaction of [(CO) 5 M Ä/C(NMe 2) Ã/C Å/CH] (M 0/Cr [1b], Mo [1c]) with n-BuLi and [W(CO) 6 ] in THF. These results demonstrate the facile migration of carbonylmetal fragments along a carbon chain. When 1a is sequentially treated with n-BuLi, [W(CO) 6 ], and water in Et 2 O Á/THF (5:1) a binuclear nonacarbonyl m-3-dimethylaminocyclobuten-2-on-1-ylidene complex [(CO) 5 W{ m-/ ae CÃCH ÄC(NMe 2)ÃC /(Ä/O)}W(CO) 4 ] (6) is produced. In solution 6 decomposes to give 2. The structures of the complexes 2 and 6 were established by X-ray structure analyses.

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Polynuclear Complexes with Propynylidene C3-Bridges: General Synthetic Route to Bis-, Tris-, and Tetrakis(ethynylcarbene) Complexes

Cited by 9 publications

References 0 publications

Binuclear Gold(I) and Mercury(II) Derivatives of Diethynylfluorenes

Binuclear Gold(I) and Mercury(II) Derivatives of Diethynylfluorenes

Bimetallic Complexes with Conjugated C₄, C₆, C₁₀, and C₁₄ Bridges: Synthetic Routes to Alkynediyl-Bridged Bis(carbene) Complexes

Mono- and binuclear 3-amino cyclobuten-2-one complexes of tungsten—facile migration of pentacarbonylmetal fragments in carbene complexes

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Polynuclear Complexes with Propynylidene C3-Bridges: General Synthetic Route to Bis-, Tris-, and Tetrakis(ethynylcarbene) Complexes

Cited by 9 publications

References 0 publications

Binuclear Gold(I) and Mercury(II) Derivatives of Diethynylfluorenes

Binuclear Gold(I) and Mercury(II) Derivatives of Diethynylfluorenes

Bimetallic Complexes with Conjugated C4, C6, C10, and C14 Bridges: Synthetic Routes to Alkynediyl-Bridged Bis(carbene) Complexes

Mono- and binuclear 3-amino cyclobuten-2-one complexes of tungsten—facile migration of pentacarbonylmetal fragments in carbene complexes

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Bimetallic Complexes with Conjugated C₄, C₆, C₁₀, and C₁₄ Bridges: Synthetic Routes to Alkynediyl-Bridged Bis(carbene) Complexes