@article {2592,
	title = {Toward Alkane Functionalization Effected with Cp*W(NO)(alkyl)(eta(3-)allyl) Complexes},
	journal = {Organometallics},
	volume = {28},
	number = {15},
	year = {2009},
	note = {ISI Document Delivery No.: 476PYTimes Cited: 2Cited Reference Count: 32Semproni, Scott P. Graham, Peter M. Buschhaus, Miriam S. A. Patrick, Brian O. Legzdins, Peter},
	month = {Aug},
	pages = {4480-4490},
	type = {Article},
	abstract = {Cp*W(NO)(n-alkyl)(eta(3)-allyl) complexes result from the selective activations of the terminal C-H bonds of alkanes. Consequently, the reactions of prototypical members of this family of complexes with a range of electrophilers and nucleophiles have been explored with a view to developing methods for functionalizing the newly formed alkyl ligands. The two principal complexes investigated in this regard have been Cp*W(NO)CH2SiMe3)(eta(3)-CH2CHCHMe) (1) and Cp*W(NO)(CH2C6H5)-(eta(3)-CH2CHCHMe) (2). In has been found that treatment of 1 and 2 with the oxidant I-2 at - 60 degrees C produces Cp*W(NO)I-2 and terminallly functionalized ICH2SiMe3 and ICH2C6H5, respectively. Oxidation of 1 by H2O2 also results in the loss of the allyl ligand and production of known oxo peroxo complex Cp*W(O)(eta(2)-O-2)(CH2SiMe3). Treatment of 1 and 2 with electrophiles affords the products resulting from addition of the electrophile to the electron-rich terminus of the sigma(-)pi distorted allyl ligands in the reactants. Thus, reagents of the type E-X (E = triphenylcarbenium, H. catecholborane; X = Cl, BF4) liberate CH3CH = CHCH2E and form the organometallic products Cp*W(NO)(X)(CH2SiMe3) and cp*W(NO)(X)(CH2C6H5), respectively. Exposure of the tungsten alkyl allyl complexes to isocyanide reagents leads to the formation of complexes insertion of isocyanide into the tungsten-allyl linkages. For instance, reaction of 1 with 2,6-xylylisocyanide produces Cp*w-(NO)(CH2SiMe3)(eta(2)-CH3CH2CHCHC = NC6H3Me2) (4b). A similar reaction of 2 with 2.6-xylylisocyanide affords both unconjugated and conjugated isocyanide insertion products, while treatment of 2 with n-butylisocyanide produces primarily the conjugated product. Finally. exposure of these tungsten alkyl allyl complexes to 1000 psi of CO gas generally results in the desired migratory insertion of the CO into the metal-alkyl linkages to form acyl compounds. Hence, 1 is first converted into Cp*W(NO)-(C(O)CH2SiMe3)(eta 3-CH2CHCHMe), which then subsequently transforms into isolable Cp*W(NO)-(C(O)CH3)(eta 3-CH2CHCHMe) (7). Interestingly, 2 does not react with CO under these experimental conditions. Nevertheless, the generality of this mode of reactivity is established by the fact that similar treatment of four other Cp*(W)(NO)(CH2CMe3)(eta(3)-allyl) complexes with CO gas at elevated pressures does afford the corresponding acyl products (8-11). All new organometallic complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of several compounds have been established by X-ray crystallographic analyses.},
	keywords = {ALLYL LIGANDS, CHEMISTRY, H BOND ACTIVATION, MOLYBDENUM, REACTIVITY},
	isbn = {0276-7333},
	url = {<Go to ISI>://000268455900035},
	author = {Semproni, S. P. and Graham, P. M. and Buschhaus, M. S. A. and Patrick, B. O. and Legzdins,Peter}
}
@article {879,
	title = {Reactivity of (trimpsi)V(NO)X-2 complexes (X = Cl, Br, I; trimpsi = (BuSi)-Bu-t(CH2PMe2)(3)). Synthesis of the first group 5 alkyl nitrosyls},
	journal = {Organometallics},
	volume = {23},
	number = {4},
	year = {2004},
	note = {ISI Document Delivery No.: 772ZFTimes Cited: 4Cited Reference Count: 40},
	month = {Feb},
	pages = {657-664},
	type = {Article},
	abstract = {Treatment of (trimpsi)V(NO)Cl-2 (trimpsi = (BuSi)-Bu-t(CH2PMe2)(3)) in NEt3 with 2 equiv each of p-toluic acid and Proton Sponge affords lemon yellow (trimpsi)V(NO)(eta(1)-O2C-4-C6H4Me)(2) (1) in 47\% isolated yield. Similarly, reaction of (trimpsi)V(NO)Cl-2 with 2 equiv of AgOTf in CH2Cl2 provides lemon yellow (trimpsi)V(NO)(OTf)(2) (2) in a comparable yield. Alternatively, 2 can be obtained directly in 40\% yield by treating CH2Cl2 solutions of (trimpsi)V(CO)(2)(NO) at -60 degreesC with 2 equiv of AgOTf. Likewise, both benzoyl peroxide and diphenyl disulfide are capable of oxidizing (trimpsi)V(CO)(2)(NO) under similar conditions to form (trimpsi)V(NO)X-2-type complexes, namely (trimpsi)V(NO)(O2CPh)(2) (3) and (trimpsi)V(NO)(SPh)(2) (4), respectively. The reactions of (trimpsi)V(NO)X-2 (X = Cl, Br) with Mg(CH2SiMe3)(2)(.)x(dioxane) (either 0.5 equiv or an excess) in THF afford the orange-red alkyl complexes (trimpsi)V(NO)(CH2SiMe3)X (X = Cl (5), Br (6)) in reasonable yields. Other members of this family of complexes such as (trimpsi)V(NO)(CH2CMe3)Cl (7) and (trimpsi)V(NO)(Me)Cl (8) can also be obtained by employing similar metathetical methodology, but all attempts to synthesize (trimpsi)V(NO)(alkyl)2 complexes have to date been unsuccessful. All new complexes have been fully characterized by standard methods, and the solid-state molecular structures of 1(.)1.5C(6)H(5)Me and 5(.)2C(4)H(8)O have been established by single-crystal X-ray diffraction analyses.},
	keywords = {CHEMISTRY, CP{\textquoteright}M(NO)R2, CRYSTAL-STRUCTURES, DERIVATIVES, H BOND ACTIVATION, MOLYBDENUM, THERMAL-ACTIVATION, TUNGSTEN, V METAL-CARBONYLS, VANADIUM},
	isbn = {0276-7333},
	url = {<Go to ISI>://000188872700007},
	author = {Hayton, T. W. and Patrick, B. O. and Legzdins,Peter}
}
@article {4052,
	title = {The versatility of lithium reagents in synthetic organometallic chemistry: Their differing reactions with [(CpMo)-Mo-*(NO)(CH2SiMe3)(2)]},
	journal = {Chemistry-a European Journal},
	volume = {3},
	number = {10},
	year = {1997},
	note = {ISI Document Delivery No.: YA856Times Cited: 13Cited Reference Count: 44},
	month = {Oct},
	pages = {1579-1587},
	type = {Article},
	abstract = {[Cp*Mo(NO)(CH2SiMe3)(2)] exhibits three principal types of reaction with the various lithium reagents investigated during this study, namely: regioselective deprotonation, reduction, and addition. Deprotonation of the reactant, achieved by treatment with lithium amide reagents, leads ultimately to the formation of the alkylidene {\textquoteright}{\textquoteright}ate{\textquoteright}{\textquoteright} complex [Cp*Mo(NO)(CH2SiMe3)(=CHSiMe3)](2)[Li-2(thf)(3)] (1). While LiN(SiMe3)(2) effects this conversion directly with no detectable intermediates, reaction with 1 equiv of LDA in THF for 15 min deprotonates the Cp* ligand to form the lithium salt of the {\textquoteright}{\textquoteright}tucked-in{\textquoteright}{\textquoteright} ate complex [(eta(5),eta(1)C(5)Me(4)CH(2))Mo(NO)(CH2SiMe3)(2)][Li(thf)(3)] (2) in 40\% isolated yield, Complex 2 slowly converts to the thermodynamically more stable 1 when left as a THF or C6D6 solution at ambient temperature fbr 48 h. Reaction of the dialkyl starting material with either tBuLi or PhLi leads to the production of the alkylidene complex 1 in irreproducible yields (10-50\% NMR; not isolable). A kinetic analysis of the reaction of [Cp*Mo(NO)(CH2SiMe3)(2)] with LiN(SiMe3)(2) indicated that the reaction was first-order in both the lithium and molybdenum reagents, and the activation parameters of Delta H-double dagger = 7,3 +/- 1.0 kcal mol(-1) and Delta S (double dagger) = -34 +/- 3 e.u. suggest an associative process. Treatment of the neutral dialkyl with 1 equiv of LiPPh2, in THF results in a one-electron reduction and production of {[Cp*Mo(NO)(CH2SiMe3)(2)][Li(thf)]}(2) (3). If left in solution, the 17e(-) dialkyl anion 3 is converted to the 18e(-) alkylidene anion 1 by the Ph2P-PPh2 coproduct, which effects the requisite hydrogen-atom abstraction. Finally, addition of a sterically undemanding alkyllithium reagent such as MeLi to the 16e(-) dialkyl reactant leads to the formation of the 18e(-) trialkyl anionic complex [Cp*Mo(NO)(CH2SiMe3)(2)(Me)][Li(thf)(3)] (4). Warming of 4 in a C6D6 solution results in loss of methane and production of 1. In most cases, the chemistry exhibited by the Mo system is duplicated by the analogous W congener, [Cp*W(NO)(CH2SiMe3)(2)]. The solid-state molecular structures of complexes 1 and 4 have been established by single-crystal X-ray crystallographic analyses.},
	keywords = {COMPLEXES, H BOND ACTIVATION, LIGAND, lithium, LIVING POLYMERIZATION, {ALKYLIDENE COMPLEXES},
	isbn = {0947-6539},
	url = {<Go to ISI>://A1997YA85600004},
	author = {Legzdins,Peter and Sayers, S. F.}
}
@article {3739,
	title = {Novel synthetic routes to the anionic alkylidene complex [Cp*Mo(NO)(CH(2)SiMe(3))(=CHSiMe(3))](-) from its neutral dialkyl precursor},
	journal = {Organometallics},
	volume = {15},
	number = {19},
	year = {1996},
	note = {ISI Document Delivery No.: VH293Times Cited: 13Cited Reference Count: 38},
	month = {Sep},
	pages = {3907-3909},
	type = {Article},
	abstract = {Conversion of the dialkyl nitrosyl complex Cp*Mo(NO)(CH(2)SiMe(3))(2) (1) to the lithium salt of the anionic alkylidene complex [Cp*Mo(NO)(CH(2)SiMe(3))(=CHSiMe(3))](2)[Li-2(THF)(3)] (2) may be effected with each of the lithium reagents LiN(SiMe(3))(2), LDA, or LiPPh(2). Interestingly, each transformation follows a different mechanistic pathway.},
	keywords = {DERIVATIVES, H BOND ACTIVATION, LIGAND, lithium, {DECOMPOSITION},
	isbn = {0276-7333},
	url = {<Go to ISI>://A1996VH29300002},
	author = {Legzdins,Peter and Sayers, S. F.}
}
