Novel η1-alkynyl zirconium porphyrin complexes: synthesis and characterization of (por)Zr(η1-CCR)3Li(THF) [por = octaethylporphyrinato (oep) or tetraphenylporphyrinato dianion (tpp); R = Ph, SiMe3]

Kim, Hee-Joon; Jung, Sungkyung; Jeon, You‐Moon; Whang, Dongmok; Kim, Kimoon

doi:10.1039/a901923e

Cited by 11 publications

(5 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The interaction could involve both acetylido C atoms (η 2 ), but as the α-C atom formally carries the negative charge of the deprotonated acetylene, the contact with the alkali metal cation will be strongest at the α-C junction. Table surveys these CC−M bond angles for 5 − 8 and those of related crystallographically characterized bimetallic alkali metal-based phenylacetylides. ,,– The aforementioned cadmium homologue to 7 is also included. A number of interesting observations can be made from the comparative data.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structural Authentication, and Structurally Defined Metalation Reactions of Lithium and Sodium DA-Zincate Bases (DA = diisopropylamide) with Phenylacetylene

Clegg

García‐Álvarez

et al. 2008

Organometallics

View full text Add to dashboard Cite

In a study aimed at developing the diisopropylamido (DA) chemistry of zincates, the new lithium DA-zincate [(TMEDA) • Li( t Bu)(DA)Zn( t Bu)] (4) has been synthesized by an interlocking cocomplexation approach comprising mixing of its three component chemicals, LDA, t Bu 2 Zn, and TMEDA, in a 1:1:1 ratio in hexane solution. Previously made by transamination from the corresponding TMP-zincate, the known sodium congener [(TMEDA) • Na( t Bu)(DA)Zn( t Bu)] (2) was also synthesized by this approach, substituting NaDA for LDA. Closely resembling each other, their molecular structures determined by X-ray crystallography can be categorized as contact ion-pair ates of TMEDA-chelated alkali metal cations linked to trigonal-planar dialkyl-Zn anions via bridging DA ligands. Reaction of 4 and 2 with phenylacetylene affords the bimetallic acetylides [{(TMEDA) • Li(CtCPh) 2 Zn( t Bu)} 2 • (TMEDA)] ( 5) and [{(TMEDA) • Na(CtCPh) 2 Zn( t Bu)} 2 ] (6), respectively. X-ray crystallographic studies reveal 5 is a pseudodimer (tetranuclear) with two (LiCZnC) rings linked at the Zn atoms by a bridging, nonchelating TMEDA ligand; in contrast 6 adopts a distorted cubane of alternating PhCtC and metal (2 Na, 2 Zn) corners. For comparison, the synthesis and crystal structures of the neutral zinc complexes [(TMEDA) • Zn(CtCPh) 2 ] (7) and [(TMEDA) • Zn( t Bu)(CtCPh)] ( 8), formally components of the ate complexes 5 and 6, are also reported. In addition, the 1 H and 13 C NMR spectra of 2, 4, 5, 6, 7, and 8 recorded from solutions in C 6 D 6 are disclosed.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis, Structural Authentication, and Structurally Defined Metalation Reactions of Lithium and Sodium DA-Zincate Bases (DA = diisopropylamide) with Phenylacetylene

Clegg

García‐Álvarez

et al. 2008

Organometallics

View full text Add to dashboard Cite

show abstract

“…The metal ions in these complexes are oxophilic; thus, the preference for carboxylate or other oxygen-bearing anionic ligands. In analogy to the zirconium-(IV) porphyrinates, [19][20][21][22][23][24][25][26][27][28][29][30] which also are almost entirely OEP and TPP derivatives, much of the research on Hf(Por)L 2 compounds has centered on the organometallic chemistry 2,18, 19,22 and the potential catalytic properties. Zr(IV) has an electron configuration of [Kr], and Hf(IV) has that of [Xe] 4f, 14 so both are closed shell metal ions.…”

Section: Introductionmentioning

confidence: 99%

Routes to New Hafnium(IV) Tetraaryl Porphyrins and Crystal Structures of Unusual Phosphate-, Sulfate-, and Peroxide-Bridged Dimers

et al. 2007

View full text Add to dashboard Cite

New routes for the synthesis of mono tetraaryl porphyrinato hafnium(IV) complexes, Hf(IV)Por(L)(2), are reported, where the secondary ligands, L, are determined by the method of purification. These synthetic routes cater to the solubility of the macrocycles and provide access to Hf(IV) complexes of meso tetraaryl porphyrins bearing diverse functional groups such as phenyl, tolyl, pyridyl, pentafluorophenyl, and carboxyphenyl. The latter three derivatives significantly expand the repertoire of hafnium porphyrinates. One route refluxes the porphyrin with HfCl(4) in 1-chloronaphthalene or in a mixed solvent of 1-chloronaphthalene and o-cresol. A second, solventless method is also reported wherein the porphyrin is mixed with Hf(cp)(2)Cl(2) and heated to give the metalated porphyrin in good yields. Simultaneous purification and formation of stable porphyrinato hafnium(IV) diacetate complexes, Hf(Por)OAc(2), is accomplished by elution over silica gel using 3-5% acetic acid in the eluent. Exchange of the acetate ligands for other oxo-bearing ligands can be nearly quantitative, such as p-aminobenzoate (PABA), pentanoate (pent), or octanoate (oct). Notably, we find that two to three of a variety of small multitopic dianions such as peroxo (O(2)(-2)), SO(4)(-2), and HPO(4)(-2) serve to bridge between two Hf(Por) moieties to form stable dimers. The crystal structures of this library of Hf(Por) complexes are reported, and we note that careful analysis of crystallography data reveals (Por)Hf(micro-eta(2)-O(2))(2)Hf(Por) rather than four bridging oxo or hydroxy ions.

show abstract

“…A recent article reported that the treatment of (por)ZrCl 2 with excess LiC⋮CR produced (por)Zr(η 1 -C⋮CR) 3 Li(THF) (por = octaethylporphyrinato or tetraphenylporphyrinato dianion; R = Ph, SiMe 3 ) . The greater size and electropositivity of Zr rationalizes this difference in chemistry.…”

Section: Resultsmentioning

confidence: 99%

“…In contrast, for R = Ph only a dinuclear complex with a central 1,4-disubstituted μ-η(1,3),η(2,4)- trans , trans -butadiene unit (“zigzag-butadiyne”) between the two titanium centers was formed. Such differences are likely due to the electronic effect of the substituents on the diyne 2 Selected Bond Lengths (Å) and Bond Angles (deg) in Complex 1 Ti−C(56) 2.018(3) Ti−C(55) 2.019(3) Ti−N(1) 2.1003(19) Ti−N(3) 2.103(2) Ti−N(4) 2.109(2) Ti−N(2) 2.122(2) C(54)−C(55) 1.462(4) C(55)−C(56) 1.316(4) C(56)−C(57) 1.396(4) C(57)−C(58) 1.210(4) C(58)−C(59) 1.428(4) C(55)−Ti−N(1) 99.11(9)C(56)−Ti−C(55) 38.06(10) C(55)−Ti−N(3) 111.48(9) C(56)−Ti−N(1) 116.61(9) C(56)−Ti−N(4) 86.37(10) C(56)−Ti−N(3) 92.98(9) N(1)−Ti−N(4) 85.02(7) C(55)−Ti−N(4) 119.55(10) C(56)−Ti−N(2) 125.39(10) C(55)−Ti−N(2) 92.90(9) C(56)−C(55)−C(54) 134.1(3) C(56)−C(55)−Ti 70.91(17) C(54)−C(55)−Ti 154.9(2) C(55)−C(56)−C(57) 143.5(3) C(55)−C(56)−Ti 71.03(17) C(57)−C(56)−Ti 145.5(2) C(58)−C(57)−C(56) 175.1(3) …”

Section: Resultsmentioning

confidence: 99%

Synthesis and Molecular Structure of (TTP)Ti(1,2-η²-PhC⋮C−C⋮CPh)

2000

View full text Add to dashboard Cite

The tetratolylporphyrinato complex, (TTP)TiCl2, oxidatively couples lithium acetylide reagents (LiC⋮CR; R = Ph, SiMe3) to 1,3-butadiyne products. The reduced Ti(II) fragment scavenges the diyne to form an η2-complex involving π-bonding to only one of the alkyne units, (TTP)Ti(1,2-η2-RC⋮C−C⋮CR). Independent syntheses of the diyne complex starting from (TTP)TiCl and (TTP)Ti(η2-EtC⋮CEt) confirm the composition of the π-adduct. The lability of the butadiyne ligand in these Ti porphyrin complexes is readily demonstrated by displacement with pyridine.

show abstract

Novel η1-alkynyl zirconium porphyrin complexes: synthesis and characterization of (por)Zr(η1-CCR)3Li(THF) [por = octaethylporphyrinato (oep) or tetraphenylporphyrinato dianion (tpp); R = Ph, SiMe3]

Cited by 11 publications

References 17 publications

Synthesis, Structural Authentication, and Structurally Defined Metalation Reactions of Lithium and Sodium DA-Zincate Bases (DA = diisopropylamide) with Phenylacetylene

Synthesis, Structural Authentication, and Structurally Defined Metalation Reactions of Lithium and Sodium DA-Zincate Bases (DA = diisopropylamide) with Phenylacetylene

Routes to New Hafnium(IV) Tetraaryl Porphyrins and Crystal Structures of Unusual Phosphate-, Sulfate-, and Peroxide-Bridged Dimers

Synthesis and Molecular Structure of (TTP)Ti(1,2-η²-PhC⋮C−C⋮CPh)

Contact Info

Product

Resources

About

Novel η1-alkynyl zirconium porphyrin complexes: synthesis and characterization of (por)Zr(η1-CCR)3Li(THF) [por = octaethylporphyrinato (oep) or tetraphenylporphyrinato dianion (tpp); R = Ph, SiMe3]

Cited by 11 publications

References 17 publications

Synthesis, Structural Authentication, and Structurally Defined Metalation Reactions of Lithium and Sodium DA-Zincate Bases (DA = diisopropylamide) with Phenylacetylene

Synthesis, Structural Authentication, and Structurally Defined Metalation Reactions of Lithium and Sodium DA-Zincate Bases (DA = diisopropylamide) with Phenylacetylene

Routes to New Hafnium(IV) Tetraaryl Porphyrins and Crystal Structures of Unusual Phosphate-, Sulfate-, and Peroxide-Bridged Dimers

Synthesis and Molecular Structure of (TTP)Ti(1,2-η2-PhC⋮C−C⋮CPh)

Contact Info

Product

Resources

About

Synthesis and Molecular Structure of (TTP)Ti(1,2-η²-PhC⋮C−C⋮CPh)