Acetylene derivatives of titanocene

Alt, Helmut G.; Engelhardt, Heidi E.; Rausch, Marvin D.; Kool, Lawrence B.

doi:10.1021/ja00298a052

Cited by 62 publications

(19 citation statements)

References 3 publications

(4 reference statements)

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“…The first step for this was the oxidation of the of ansa-titanocene bis(trimethylsilyl)acetylene complexes by N 2 O to the pyridine stabilized Ti=O complexes, which was followed by hydrolysis of the Ti=O moiety, a formal 1,2-addition of water across this bond (Scheme 57). [80] Additionally, it was reported, that Cp* 2 Ti(OTf ) was prepared by oxidation of the complex Cp* 2 Ti(η 2 -btmsa) with Yb(OTf ) 3 or Fe(OTf ) 3 . This reaction is highly selective and the formation of the bis(triflate) complex Cp* 2 Ti(OTf ) 2 was not observed.…”

Section: Reactions With Water (H 2 O)mentioning

confidence: 99%

“…[1b,c] There exist several reductive metallocene [Cp′ 2 M] generating systems, for example mixtures of Cp′ 2 MCl 2 with Zn, Al, Mg and Sm [1] or the Negishi reagent Cp 2 ZrCl 2 /nBuLi. [2] Additionally, there are well defined complexes, in which the coordinatively and electronically unsaturated complex fragments [Cp′ 2 M] are stabilized in Cp′ 2 M(L) n by well suited ligands L as for example in the complexes Cp 2 Ti(PMe 3 ) 2 introduced by Rausch and Alt et al [3] Cp 2 Ti[(P(OEt) 3 ] 2 [4] and the here described complexes Cp′ 2 M(L)(η 2 -btmsa), btmsa = bis(trimethylsilyl)acetylene, with or without L such as pyridine or THF. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] There exist several methods to prepare such bis(trimethylsilyl)acetylene complexes Cp′ 2 M(η 2 -Me 3 SiC 2 SiMe 3 ) as starting materials.…”

Section: Introductionmentioning

confidence: 99%

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Recent Synthetic and Catalytic Applications of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes

Rosenthal

2019

Eur J Inorg Chem

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With the 30 years old first example of a stable group 4 metallocene bis(trimethylsilyl)acetylene (btmsa) complex Cp2Ti(η2‐btmsa) a series of similar complexes like Cp′2M(η2‐btmsa) (M = Ti, Zr; Cp′ = Cp, Cp* as η5‐pentamethylcyclopentadienyl and Cp′2 = rac‐(ebthi) as rac‐1,2‐ethylene‐1,1′‐bis(η5‐tetrahydroindenyl) ) represent excellent sources for the generation of the very reactive coordinatively and electronically unsaturated complex fragments [Cp'2M], which were used in many synthetic and catalytic reactions. Examples for this were oresented in several papers and summarized in some reviews. In this update new reactions of group 4 metallocene bis(trimethylsilyl)acetylene complexes towards symmetrically and unsymmetrically α‐dihetero‐substituted alkynes, reactions with other alkynes, di‐ and polyynes to metallacyclopentadienes as well as the conversions of the formed products are summarized. Additionally, novel synthetic applications of the formed metallacyclopentadienes on the basis of the zirconocene bis(trimethylsilyl)acetylene complex Cp2Zr(py)(η2‐btmsa) are highlighted. Reactions with imines, neutral N‐donor ligands, E‐H compounds (E = N, O, P), molecular hydrogen, water, phosphino‐ and aminoboranes, E‐Cl compounds (E = C, P), disilylated germylenes and aryloxy ketones were described. Different self‐assembly reactions to multinuclear complexes by using group 4 metallocene bis(trimethylsilyl)acetylene complexes in C‐C coupling reactions with or without C‐H bond activation to tri‐ or tetranuclear complexes are considered, too. These examples are discussed following the general L‐M‐S principle for stoichiometric and catalytic reactions, whereby different ligands L (L = Cp′ = Cp, Cp*, rac‐ebthi), metals M (M = Ti, Zr, Hf) and substrate substituents S influence the reactivity and the obtained products.

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Section: Reactions With Water (H 2 O)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Recent Synthetic and Catalytic Applications of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes

Rosenthal

2019

Eur J Inorg Chem

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“…Recently, research has been concerned with the synthesis and characterization of metallacyclic intermediates, which can be isolated with the use of appropriate metal centers and ligands around the metal and studied as independent species [57]. Metallacyclic compounds of this type are known for a wide range of transition metals, including Ti [58,59], Zr [60], Hf [61,62], Pt [63], Pd [64], Ir [50,65], Ru [66], W [67,68], Fe [69], Au [70], Rh [71] and Co [53,72]. There are a vast number of such complexes, and their more complex derivatives, and these will not be reviewed here.…”

Section: Collman Et Al Used Isotopically Labelledmentioning

confidence: 99%

Dibenzometallacyclopentadienes, boroles and selected transition metal and main group heterocyclopentadienes: Synthesis, catalytic and optical properties

Steffen

Ward

Jones

et al. 2010

Coordination Chemistry Reviews

113

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“…As mentioned above, the examples for ligand substitutions in the complexes Cp′ 2 ML 2 such as Cp 2 Ti(PMe 3 ) 2 , Cp 2 Ti(P[OEt) 3 ] 2 , [Cp* 2 Ti(N 2 )] 2 N 2 , Cp 2 Ti(CO) 2 , Cp 2 TiR 2 etc . generate the [Cp′ 2 M] fragment by a ligand exchange reaction.…”

Section: Examples For Substrate Substitutionmentioning

confidence: 99%

Advantages of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes as Metallocene Sources Towards Other Synthetically used Systems

Rosenthal

2019

ChemistryOpen

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Active species for synthetic and catalytic applications are formed from well defined complexes or mixtures of compounds. For group 4 metallocenes, three pathways for the formation of the reactive complex fragment [Cp′ 2 M] are known: (i) reductive mixtures and well defined complexes which are able to form the metallocene fragments either by (ii) addition or (iii) substitution reactions. In this account for each of theses systems (i)–(iii) a prominent example will be discussed in detail, (i) the Negishi reagent Cp 2 ZrCl 2 /n‐BuLi, (ii) bis(η 5 : η 1 ‐pentafulvene) complexes and (iii) metallocene bis(trimethylsilyl)acetylene complexes, to show the advantages and the disadvantages for each of these methods for synthetic applications. This account summarizes some main advantages of group 4 metallocene bis(trimethylsilyl)acetylene complexes as metallocene generating agents over other synthetically used systems. For each of the special purposes, all described systems have advantages as well as disadvantages. The aim of this overview is to help synthetic chemists in selecting the most effective system on the basis of [Cp′ 2 M] (M=Ti, Zr) for synthetic or catalytic puposes.

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Acetylene derivatives of titanocene

Cited by 62 publications

References 3 publications

Recent Synthetic and Catalytic Applications of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes

Recent Synthetic and Catalytic Applications of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes

Dibenzometallacyclopentadienes, boroles and selected transition metal and main group heterocyclopentadienes: Synthesis, catalytic and optical properties

Advantages of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes as Metallocene Sources Towards Other Synthetically used Systems

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