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• W2000795855 endingPage "8146" @default.
• W2000795855 startingPage "8131" @default.
• W2000795855 abstract "Reaction of the dichloro complexes [M(N(2) (TBS)N(py))Cl(2)] (M=Zr: 1, Hf: 2; TBS: tBuMe(2)Si; py: pyridine) with one molar equivalent of LiNHNPh(2) gave mixtures of the two diastereomeric chlorohydrazido(1-) complexes [M(N(2) (TBS)N(py))(NHNPh(2))Cl] (M=Zr: 3 a,b, Hf: 4 a,b) in which the diphenylhydrazido(1-) ligand adopts a bent kappa(1) coordination. This mixture of isomers could be cleanly converted into the deep green diphenylhydrazido(2-) complexes [Zr(N(2) (TBS)N(py))(NNPh(2))(py)] (5) and [Hf(N(2) (TBS)N(py))(NNPh(2))(py)] (6), respectively, by dehydrohalogenation with lithium hexamethyldisilazide (LiHMDS) in the presence of one molar equivalent of pyridine. Both complexes contain a linearly coordinated hydrazinediide for which a DFT-based frontier orbital analysis established bonding through one sigma and two pi orbitals. A high polarity of the M=N bond was found, in accordance with the description of hydrazinediide(2-) acting as a six-electron donor ligand. The pyridine ligand in [M(N(2) (TBS)N(py))(NNPh(2))(py)] (M=Zr: 5, Hf: 6) is substitutionally labile as established by line-shape analysis of the dynamic spectra (DeltaG(not equal)=19 kcal mol(-1)). A change in denticity of the hydrazido unit from kappa(1) to kappa(2) was studied by DFT methods. Both forms are calculated to be very close in energy and are only separated by shallow activation barriers, which supports the notion of a rapid kappa(1) to kappa(2) interconversion. This process is believed to happen early on in the N-N scission in the presence of coupling reagents. Frontier orbital and natural population analyses suggest that a primarily charge-controlled nucleophilic attack at N(alpha) is unlikely whereas interaction with an electrophile could play an important role. This hypothesis was tested by the reaction of 5 and 6 with one molar equivalent of B(C(6)F(5))(3) to give [Zr(N(2) (TBS)N(py))(NNPh(2)){B(C(6)F(5))(3)}] (7) and [Hf(N(2) (TBS)N(py))(NNPh(2)){B(C(6)F(5))(3)}] (8). In these products, B(C(6)F(5))(3) becomes attached to the N(alpha) atom of the side-on bound hydrazinediide and there is an additional interaction of an ortho-F atom of a C(6)F(5) ring with the metal centre." @default.
• W2000795855 created "2016-06-24" @default.
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• W2000795855 date "2008-09-15" @default.
• W2000795855 modified "2023-10-18" @default.
• W2000795855 title "Bonding and Bending in Zirconium(IV) and Hafnium(IV) Hydrazides" @default.
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• W2000795855 cites W1964135877 @default.
• W2000795855 cites W1964837435 @default.
• W2000795855 cites W1969620481 @default.
• W2000795855 cites W1972291343 @default.
• W2000795855 cites W1975217371 @default.
• W2000795855 cites W1975563186 @default.
• W2000795855 cites W1978195121 @default.
• W2000795855 cites W1980777144 @default.
• W2000795855 cites W1984599229 @default.
• W2000795855 cites W1985179168 @default.
• W2000795855 cites W1986352627 @default.
• W2000795855 cites W1990632578 @default.
• W2000795855 cites W1993383767 @default.
• W2000795855 cites W1996186038 @default.
• W2000795855 cites W1998874288 @default.
• W2000795855 cites W2000195574 @default.
• W2000795855 cites W2002194503 @default.
• W2000795855 cites W2009524394 @default.
• W2000795855 cites W2011254772 @default.
• W2000795855 cites W2013872101 @default.
• W2000795855 cites W2018463844 @default.
• W2000795855 cites W2018627913 @default.
• W2000795855 cites W2019192473 @default.
• W2000795855 cites W2020445997 @default.
• W2000795855 cites W2021026520 @default.
• W2000795855 cites W2022244698 @default.
• W2000795855 cites W2023876149 @default.
• W2000795855 cites W2027683502 @default.
• W2000795855 cites W2028632171 @default.
• W2000795855 cites W2028760273 @default.
• W2000795855 cites W2030841140 @default.
• W2000795855 cites W2032425364 @default.
• W2000795855 cites W2033451713 @default.
• W2000795855 cites W2033990154 @default.
• W2000795855 cites W2038551965 @default.
• W2000795855 cites W2038767330 @default.
• W2000795855 cites W2042944554 @default.
• W2000795855 cites W2046412723 @default.
• W2000795855 cites W2049079467 @default.
• W2000795855 cites W2051191858 @default.
• W2000795855 cites W2054463460 @default.
• W2000795855 cites W2056607244 @default.
• W2000795855 cites W2064198780 @default.
• W2000795855 cites W2068917975 @default.
• W2000795855 cites W2073030296 @default.
• W2000795855 cites W2085966856 @default.
• W2000795855 cites W2088749835 @default.
• W2000795855 cites W2091779926 @default.
• W2000795855 cites W2094642658 @default.
• W2000795855 cites W2095510108 @default.
• W2000795855 cites W2110669990 @default.
• W2000795855 cites W2114946345 @default.
• W2000795855 cites W2124808520 @default.
• W2000795855 cites W2127387930 @default.
• W2000795855 cites W2131350133 @default.
• W2000795855 cites W2143241367 @default.
• W2000795855 cites W2143981217 @default.
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• W2000795855 cites W2157241641 @default.
• W2000795855 cites W2163507847 @default.
• W2000795855 cites W2169128794 @default.
• W2000795855 cites W2170643129 @default.
• W2000795855 cites W2172487666 @default.
• W2000795855 cites W2175563762 @default.
• W2000795855 cites W2949431553 @default.
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• W2000795855 doi "https://doi.org/10.1002/chem.200800876" @default.
• W2000795855 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/18680131" @default.
• W2000795855 hasPublicationYear "2008" @default.
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