[{(C7H13N2)AlCl}2O]: Ein zweikerniger Vinamidin-Komplex des Aluminiums mit linearer Sauerstoffbrücke [1]

Abstract

C 7 H 13 N 2 )AlCl 2 ] (1) reacts with Ag 2 O in the ratio 2/1 to give the dinuclear vinamidine complex [{(C 7 H 13 N 2 )AlCl} 2 O] (2) in good yield. The crystal structure investigation of 2 reveals the presence of a linear fragment AlϪOϪAl in the centrosymmetric space group P2 1 /c.

Synthesis, Structural Characterization, and Reaction of the First Terminal Hydroxide‐Containing Alumoxane with an [{Al(OH)}2(μ‐O)] Core

“…The AlOH bond lengths (1.738(3) and 1.741(3) Å) of 3 are significantly longer than those in 1 (1.6947(15) and 1.7107(16) Å),8 but considerably shorter than those of the Al(μ‐OH) and Al(μ 3 ‐OH) bonds exhibited by compounds [(Ph 2 Si) 2 O 3 ] 4 Al 4 (μ‐OH) 4 (1.787(3) to 1.814(3) Å, average 1.800 Å),14 [{Mes 2 Al(μ‐OH)} 2 ]⋅2 THF (1.822 Å; Mes=mesityl),3e and [Al 5 ( t Bu) 5 (μ 3 ‐O) 2 (μ 3 ‐OH) 2 (μ‐OH) 2 (μ‐O 2 CPh) 2 ] (Al(μ 3 ‐OH), 1.914(5) to 2.086(4) Å; Al(μ‐OH), 1.820(3) to 1.828(3) Å) 15. The AlN bond lengths (1.912(3) and 1.928(3) Å) are longer than those observed in 1 (1.8881(17) and 1.8903(16) Å) and [{HC[(CMe)(NMe)] 2 AlCl} 2 (μ‐O)] (1.8611(16) and 1.8617(16) Å) 13…”

“…The OH groups are bent out of the Al(1)O(3)Al(2) plane (31.26° and 30.71°) towards the opposite side where the 2,6‐ i Pr 2 C 6 H 3 substituents are oriented. The Al‐(μ‐O) bond lengths (1.698(3) and 1.694(3) Å) are comparable, and the Al‐(μ‐O)‐Al angle (143.84(16)°) is significantly smaller than those found in compounds [{[(Me 3 Si) 2 HC] 2 Al} 2 (μ‐O)] (1.6877(4) Å; 180°),11 [{( t Bu) 2 Al[NH(Me)CH 2 CH 2 NMe 2 ]} 2 ](μ‐O) (1.690(7) Å; 173.0(4)°),12 and [{HC[(CMe)(NMe)] 2 AlCl} 2 (μ‐O)] (1.6770(6) Å; 180°) 13. The AlOH bond lengths (1.738(3) and 1.741(3) Å) of 3 are significantly longer than those in 1 (1.6947(15) and 1.7107(16) Å),8 but considerably shorter than those of the Al(μ‐OH) and Al(μ 3 ‐OH) bonds exhibited by compounds [(Ph 2 Si) 2 O 3 ] 4 Al 4 (μ‐OH) 4 (1.787(3) to 1.814(3) Å, average 1.800 Å),14 [{Mes 2 Al(μ‐OH)} 2 ]⋅2 THF (1.822 Å; Mes=mesityl),3e and [Al 5 ( t Bu) 5 (μ 3 ‐O) 2 (μ 3 ‐OH) 2 (μ‐OH) 2 (μ‐O 2 CPh) 2 ] (Al(μ 3 ‐OH), 1.914(5) to 2.086(4) Å; Al(μ‐OH), 1.820(3) to 1.828(3) Å) 15.…”

Aluminum Dihydroxide with Terminal OH Groups: An Unprecedented Congener of Boronic Acid

“…[14] However, The AlÀOH bond lengths of 2 are comparable to those of the AlÀ(m-O) bonds in [(HC{(CMe)(NMe)} 2 AlCl) 2 (m-O)] (1.6770(6) ) [15] and [{(tBu) 2 Al(NH(Me)CH 2 CH 2 NMe 2 )} 2 (m-O)] (1.690(7) and 1.714(7) ), [16] in which the linear or almost linear {Al 2 (m-O)} cores lead to the significant double-bond (16) and 1.8617(16) ), [15] and similar to those in [LAl(SeH) 2 ] (1.8996(6) ). [17] Ab initio [18] calculations were carried out to investigate the intermolecular hydrogen bonding and the electronic structure of 2.…”

Development in the Theory of Cationoid Polymerisation

“…However, The AlOH bond lengths of 2 are comparable to those of the Al(μ‐O) bonds in [(HC{(CMe)(NMe)} 2 AlCl) 2 (μ‐O)] (1.6770(6) Å)15 and [{( t Bu) 2 Al(NH(Me)CH 2 CH 2 NMe 2 )} 2 (μ‐O)] (1.690(7) and 1.714(7) Å),16 in which the linear or almost linear {Al 2 (μ‐O)} cores lead to the significant double‐bond character of the AlO bonds. The AlN bond lengths (1.8881(17) and 1.8903(16) Å) are longer than those observed in [(HC{(CMe)(NMe)} 2 AlCl) 2 (μ‐O)] (1.8611(16) and 1.8617(16) Å),15 and similar to those in [LAl(SeH) 2 ] (1.8996(6) Å) 17…”

“…The AlOH bond lengths (1.6947(15) and 1.7107(16) Å) are significantly shorter than those of the Al(μ‐OH) and Al(μ 3 ‐OH) bonds in [{(Ph 2 Si) 2 O 3 } 4 Al 4 (μ‐OH) 4 ] (1.787(3) to 1.814(3) Å, av 1.800 Å),13 [Mes 2 Al(μ‐OH)] 2 ⋅2 THF (1.822 Å; Mes=mesityl),5 and [Al 5 ( t Bu) 5 (μ 3 ‐O) 2 (μ 3 ‐OH) 2 (μ‐OH) 2 (μ‐O 2 CPh) 2 ] (Al(μ 3 ‐OH) 1.914(5) to 2.086(4) Å; Al(μ‐OH) 1.820(3) to 1.828(3) Å) 14. However, The AlOH bond lengths of 2 are comparable to those of the Al(μ‐O) bonds in [(HC{(CMe)(NMe)} 2 AlCl) 2 (μ‐O)] (1.6770(6) Å)15 and [{( t Bu) 2 Al(NH(Me)CH 2 CH 2 NMe 2 )} 2 (μ‐O)] (1.690(7) and 1.714(7) Å),16 in which the linear or almost linear {Al 2 (μ‐O)} cores lead to the significant double‐bond character of the AlO bonds. The AlN bond lengths (1.8881(17) and 1.8903(16) Å) are longer than those observed in [(HC{(CMe)(NMe)} 2 AlCl) 2 (μ‐O)] (1.8611(16) and 1.8617(16) Å),15 and similar to those in [LAl(SeH) 2 ] (1.8996(6) Å) 17…”