Ancillary aryloxide ligands in ethylene polymerization catalyst precursors

Preparation of Diamidochloro(cyclopentadienyl)titanium Derivatives as Pre‐Catalysts for Olefin Polymerization − X‐ray Molecular Structure of [Ti(η5‐C5H5){1,2‐C6H4(NCH2CH2CH3)2}Cl] and [Ti{η5‐C5H4(SiMe3)}{1,2‐C6H4(NCH2CH2CH3)2}Cl]

“…We assume that initially the MAO cocatalyst reacts with these complexes by methylϪhalide exchange to afford TiϪMe derivatives, followed by cleavage of one of the TiϪN bonds by the AlMe 3 component in the MAO cocatalyst to generate active cationic alkyl species in a ZieglerϪNatta olefin polymerization model. [27] …”

“Isomerism” of Coordination Modes and Numbers in Pentanuclear Organozinc Hydroxylamides: An Exercise in Subtle Substituent Size Effects

“…In metal alkoxide/aryloxide chemistry, [1] an increase in aggregate dimensionality is already well established [compare the Al 2 O 2 ring {(Me 2 Al)[O(2,6-iPr 2 -C 6 H 3 )]} 2 [2] with the "double cube" [(MeZn) 3 (OMe) 4 ] 2 Zn [3] (CN = 4, 6)]. [4] The highly diverse chemistry of the O-N double-donor array (hydroxylamines or oximes) provides a plethora of aggregation motifs, for example in group 13 complexes, [5][6][7][8][9] and ought to be transferable to zinc for the exploration of similar extensions {compare the six-membered ring dimer [(Me 2 Al)(ON=CMe 2 )] 2 [5a,5b] with the tetrahedroid oximate [(MeZn)(ON=CMe 2 )] 4 [10] (CN = 4)}.…”

Structural Effects of Varied Steric Bulk in 2,(4),6‐Substituted Dimethylthallium(III) Phenoxides

“…It should be noted that [Me 2 AlO(2,6-R 2 C 6 H 3 )] 2 [R = iPr, Ph] have C Me -Al-C Me bond angles in the 114.3(6)-116.9(2)°range, whereas [Me 2 -InO(2,6-Me 2 C 6 H 3 )] 2 has a C Me -In-C Me bond angle of 131.0(2)°. [22][23][24] Therefore, the (acute) calculated C Me -Tl-C Me angles are still significantly greater than those observed for structurally characterized aluminum and indium analogues. The difference is even more significant in the monomeric structures, in which the C Me -In-C Me bond angle of [Me 2 InO(2,4,6-tBu 3 C 6 H 2 )] is 109.3(8)°and the C Me -Tl-C Me bond angle of 8 is 170.2(2)°.…”

“…The overall structural arrangement of 5 is similar to that of the indium analogue [Me 2 InO(2,6-Me 2 C 6 H 3 )] 2 , [22] whereas 6 resembles the aluminum analogue [Me 2 AlO(2,6-iPr 2 C 6 H 3 )] 2 . [23] Contrary to the decrease in the C Me -Tl-C Me bond angle observed in 5 and 6, that of the 2,6-diphenylphenoxide analogue 7 [C1-Tl1-C2 169.1(2)°and C3-Tl1-C4 171.9(2)°] was found to be greater than in 4-6 [156.9(2)°and Finally, the 2,6-diphenyl substituents are rotated with respect to the central phenoxide rings, presumably to allow for minimum steric repulsion with the (Me 2 TlO) 2 core, as well as between 2,6-Ph 2 C 6 H 3 O groups. The structure of 7 differs from that of the aluminum analogue [Me 2 AlO(2,6-Ph 2 C 6 H 3 )] 2 , which has a structural arrangement similar to 5 and 6.…”