Aspinall Helen C, Bickley Jamie F, Gaskell Jeffrey M, Jones Anthony C, Labat Gael, Chalker Paul R, Williams Paul A
Department of Chemistry, Donnan and Robert Robinson Laboratories, University of Liverpool, Crown Street, Liverpool L69 7ZD, UK.
Inorg Chem. 2007 Jul 23;46(15):5852-60. doi: 10.1021/ic061382y. Epub 2007 Jun 20.
Complexes of the early lanthanides with the donor-functionalized alkoxide ligand mmp (Hmmp = HOCMe(2)CH(2)OMe, 1-methoxy-2-methylpropan-2-ol) are excellent precursors for Metal Organic Chemical Vapor Deposition (MOCVD) and Atomic Layer Deposition (ALD) of lanthanide oxides; however, their coordination chemistry, which is the subject of this paper, is rather complex. Precursors for MOCVD and ALD of lanthanide oxides are prepared by the reaction of [Ln{N(SiMe(3))(2)}(3)] with 3 equiv of the alcohol Hmmp in toluene in the presence of 1 equiv of tetraglyme and are indefinitely stable in solution. Reaction of [Ln{N(SiMe(3))(2)}(3)] with 3 equiv of Hmmp in the absence of stabilizing Lewis bases gives complex condensed products with empirical formula [{Ln(mmp)(3-n)}(2)O(n)]. These condensed products show poor volatility and are unsatisfactory precursors for MOCVD or ALD of oxides. The cluster complex [La(3)(mu(3),kappa(2)-mmp)(2)(mu(2),kappa(2)-mmp)(3)(mmp)(4)] has been prepared by careful reaction of [La{N(SiMe(3))(2)}(3)] with 4 equiv of Hmmp and has been characterized by single-crystal X-ray diffraction. Salt metathesis reactions using M(mmp) (M = Li or Na) are unreliable routes to [Ln(mmp)(3)]. Crystals of the heterometallic cluster complex [NaLa(3)(mu(3)-OH)(mu(3),kappa(2)-mmp)(2)(mu(2),kappa(2)-mmp)(4)(mmp)(3)] were isolated from the reaction of [La(NO(3))(3)(tetraglyme)] with 3 equiv of Na(mmp), and crystals of [Li(kappa(2)-Hmmp)Pr(mu(2),eta(2)-mmp)(4))LiCl] were isolated from the reaction of PrCl(3) with 3 equiv of Li(mmp); both of these complexes have been characterized by single-crystal X-ray diffraction.
早期镧系元素与供体官能化醇盐配体mmp（Hmmp = HOCMe(2)CH(2)OMe，1-甲氧基-2-甲基-2-丙醇）形成的配合物是用于镧系元素氧化物的金属有机化学气相沉积（MOCVD）和原子层沉积（ALD）的优良前驱体；然而，本文所讨论的它们的配位化学相当复杂。镧系元素氧化物的MOCVD和ALD前驱体是通过在1当量四甘醇存在下，使[Ln{N(SiMe(3))(2)}(3)]与3当量醇Hmmp在甲苯中反应制备的，并且在溶液中无限稳定。在没有稳定的路易斯碱存在下，[Ln{N(SiMe(3))(2)}(3)]与3当量Hmmp反应生成具有经验式[{Ln(mmp)(3 - n)}(2)O(n)]的复杂缩合产物。这些缩合产物挥发性差且是用于氧化物MOCVD或ALD的不理想前驱体。簇合物[La(3)(μ(3),κ(2)-mmp)(2)(μ(2),κ(2)-mmp)(3)(mmp)(4)]是通过使[La{N(SiMe(3))(2)}(3)]与4当量Hmmp小心反应制备的，并通过单晶X射线衍射进行了表征。使用M(mmp)（M = Li或Na）的盐复分解反应是制备[Ln(mmp)(3)]不可靠的途径。从[La(NO(3))(3)(四甘醇)]与3当量Na(mmp)的反应中分离出异金属簇合物[NaLa(3)(μ(3)-OH)(μ(3),κ(2)-mmp)(2)(μ(2),κ(2)-mmp)(4)(mmp)(3)]的晶体，从PrCl(3)与3当量Li(mmp)的反应中分离出[Li(κ(2)-Hmmp)Pr(μ(2),η(2)-mmp)(4))LiCl]的晶体；这两种配合物均通过单晶X射线衍射进行了表征。
