Synthesis and reactivity of bis-alkynyl appended metallocenes of Ti, Fe, and Co

2010 ◽  
Vol 88 (12) ◽  
pp. 1213-1221 ◽  
Author(s):  
Preeti Chadha ◽  
Jason L. Dutton ◽  
Paul J. Ragogna
Keyword(s):  
Transition Metal ◽  
Single Crystal ◽  
Structure Analysis ◽  
Late Transition Metal ◽  
Metal Halides ◽  
X Ray ◽  
Metal Atoms ◽  
Late Transition

(Dimethyl)(phenylethynyl)silyl-substituted cyclopentadiene C5H5SiMe2C2Ph (1) was synthesized by the reaction of in situ generated C5H5SiMe2Cl with LiC2Ph. Metallation of 1 with nBuLi or KN(SiMe3)2 gave the corresponding Li (2) and K (3) salts. Transmetallation of 2 with transition metal halides MCl2 (M = TiCl2, Fe, and Co) generated the corresponding early and late transition metal metallocenes (4, 5, and 6) with pendant alkynyl substituents. Compounds 4 and 6 are the first examples of bis alkyne appended Ti and Co metallocenes. Complexes 5 and 6 undergo alkyne dimerization in the presence of CpCo(CO)2 generating metallocenophanes 7 and 8 incorporating two metal atoms. Compounds 3, 4Cl2, 6, and [8][OTf] have been characterized by single crystal X-ray structure analysis.

Synthesis of an iridium porphyrin amido complex

2011 ◽  
Vol 89 (12) ◽  
pp. 1506-1511 ◽  
Author(s):  
Jenkins Yin Ki Tsang ◽  
Kin Shing Chan
Keyword(s):  
Transition Metal ◽  
Late Transition Metal ◽  
Synthetic Route ◽  
Amido Complexes ◽  
X Ray ◽  
Pyridine Solution ◽  
Aqueous Mixture ◽  
Late Transition ◽  
Established Treatment

A synthetic route for iridium porphyrin amido complexes has been established. Treatment of a THF solution of Ir(ttp)(CO)Cl (1) (ttp = 5,10,15,20-tetrakis(p-tolyl)porphyrinato dianion) with an aqueous mixture of NaOH and NaBH4, followed by 2-iodoethanol leads to the clean formation of the β-hydroxyethyl complex Ir(ttp)(C2H4OH) (2) in 92% yield. Heating a pyridine solution of complex 2 in the presence of ca. 5–10 equiv. of phthalimide (HNC8H4O2; HPhth) leads to the formation of Ir(ttp)(C5H5N)(CH2CH2Phth) (3). The replacement of pyridine by THF as the reaction solvent leads to the formation of the THF adduct Ir(ttp)(THF)(Phth) (4), which has been characterized spectroscopically. Heating a solution of 4 in pyridine leads to the formation of Ir(ttp)(C5H5N)(Phth) (5), which has been isolated in 72% yield. Complexes 3 and 5 have been characterized by X-ray crystallographic studies. Complexes 4 and 5 are rare examples of monomeric late transition metal-amido complexes and are the first examples of iridium-amido complexes featuring a porphyrin as a supporting ligand.

Alkane activation on crystalline metal oxide surfaces

2014 ◽  
Vol 43 (22) ◽  
pp. 7536-7547 ◽  
Author(s):  
Jason F. Weaver ◽  
Can Hakanoglu ◽  
Abbin Antony ◽  
Aravind Asthagiri
Keyword(s):  
Transition Metal ◽  
Metal Oxide ◽  
Bond Activation ◽  
Oxide Surfaces ◽  
Late Transition Metal ◽  
Alkane Activation ◽  
Metal Oxide Surfaces ◽  
Metal Atoms ◽  
Late Transition ◽  
Crystalline Metal

Late transition-metal oxide surfaces that expose coordinatively-unsaturated metal atoms promote the formation and bond activation of alkane σ-complexes.

Synthesis, structural characterization, and reactivity of late transition-metal complexes bearing linked cyclopentadienyl–carboranyl ligands

2012 ◽  
Vol 90 (1) ◽  
pp. 108-117 ◽  
Author(s):  
Dongmei Liu ◽  
Zaozao Qiu ◽  
Hoi-Shan Chan ◽  
Zuowei Xie
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Structural Characterization ◽  
Molecular Structures ◽  
Spectroscopic Techniques ◽  
Late Transition Metal ◽  
X Ray ◽  
Elemental Analyses ◽  
Late Transition

Late transition-metal complexes bearing linked cyclopentadienyl/indenyl–carboranyl ligands were synthesized and their reactivities were examined. Reaction of Li2[Me2C(L)(C2B10H10)] (L = C5H4, C9H6, Me2NCH2CH2C5H3) with MCl2(PPh3)2 in Et2O afforded [η5:σ-Me2C(C5H4)(C2B10H10)]M(PPh3) (M = Co (4), Ni (5)), [η5:σ-Me2C(C9H6)(C2B10H10)]M(PPh3) (M = Co (6), Ni (7)), and [η5:σ-Me2C(Me2NCH2CH2C5H3)(C2B10H10)]Ni(PPh3) (8). Treatment of 4 or 5 with 2,6-dimethylphenylisocyanide, N-heterocyclic carbene (NHC), PCy3, or 1,2-bis(diphenylphosphino)ethane (dppe) gave the corresponding PPh3 displacement complexes [η5:σ-Me2C(C5H4)(C2B10H10)]M(2,6-Me2C6H3NC) (M = Co (9), Ni (10)), [η5:σ-Me2C(C5H4)(C2B10H10)]M[1,3-(2,6-i-Pr2C6H3)2C3N2H2] (M = Co (11), Ni (12)), [η5:σ-Me2C(C5H4)(C2B10H10)]Ni(PCy3) (13), or {[η5:σ-Me2C(C5H4)(C2B10H10)]Co}2(dppe) (14), respectively. These complexes were characterized by various spectroscopic techniques and elemental analyses. The molecular structures of 4–14 were further confirmed by single-crystal X-ray analyses.

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