Off-the-Shelf Gd(NO3)3 as an Efficient High-Spin Metal Ion Polarizing Agent for Magic Angle Spinning Dynamic Nuclear Polarization.

Magic angle spinning nuclear magnetic resonance spectroscopy experiments are widely employed in the characterization of solid media. The approach is incredibly versatile but deleteriously suffers from low sensitivity, which may be alleviated by adopting dynamic nuclear polarization methods, resulting in large signal enhancements. Paramagnetic metal ions such as Gd3+ have recently shown promising results as polarizing agents for 1H, 13C, and 15N nuclear spins. We demonstrate that the widely available and inexpensive chemical agent Gd(NO3)3 achieves significant signal enhancements for the 13C and 15N nuclear sites of [2-13C,15N]glycine at 9.4 T and ∼105 K. Analysis of the signal enhancement profiles at two magnetic fields, in conjunction with electron paramagnetic resonance data, reveals the solid effect to be the dominant signal enhancement mechanism. The signal amplification obtained paves the way for efficient dynamic nuclear polarization without the need for challenging synthesis of Gd3+ polarizing agents.

A hybrid nanoparticle/alkoxide ink for inkjet printing of TiO2: a templating effect to form anatase at 200 °C.

A reactive ink (Ink 1) containing Ti(OPri)4 in PriOH with dimethoxyethan as a kinetic stabiliser deposits TiO2 by inkjet printing. A hybrid ink (Ink 2) consists of Ink 1 with the addition of anatase NPs, which act as seeds for the formation of anatase TiO2 at 200 °C. Printing of anatase on PET is also reported.

Adding the right (or left) twist to tris-chelate complexes--coordination chemistry of chiral oxazolylphenolates with M3+ ions (M = Al or lanthanide).

A series of homoleptic tris-chelate complexes ML3 (M = Al or rare earth; L = chiral or achiral oxazolyl phenolate or -naphtholate) is reported. In all cases, complexes crystallize as mer-isomers and complete diastereoselectivity is observed on crystallization of the complexes: ML3 crystallize with Λ-helicity at the metal where L = (S)-oxazolylphenolate. Complexes have been characterized in solution by NMR spectroscopy, demonstrating rapid ligand exchange at ambient temperature for rare earth complexes, and slow exchange on the NMR timescale for complexes of Al; in all cases the mer-isomer is observed exclusively. Crystal structures are reported for [YL3]2 (L = (S)-2-(4-isopropyl-4,5-dihydrooxazol-2-yl)-phenolate), mer-[YbL3] (L = (S)-2-(4-isopropyl-4,5-dihydrooxazol-2-yl)-6-methylphenolate) and mer-[AlL3] (L = (S)-2-(4-isopropyl-4,5-dihydrooxazol-2-yl)-6-methylphenolate, L = (S)-2-(4-isopropyl-4,5-dihydrooxazol-2-yl)-6-cyanophenolate), L = (S)-1-(4-isopropyl-4,5-dihydrooxazol-2-yl)naphthalen-2-olate, L = 1-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)naphthalen-2-olate).

Ce(IV) complexes with donor-functionalized alkoxide ligands: improved precursors for chemical vapor deposition of CeO2.

Thin films of ceria (CeO(2)) have many applications, and their synthesis by liquid-injection MOCVD (metal-organic chemical vapor deposition) or ALD (atomic layer deposition) requires volatile precursor compounds. Here we report the synthesis of a series of homoleptic and heteroleptic Ce(IV) complexes with donor-functionalized alkoxide ligands mmp (1-methoxy-2-methylpropan-2-olate), dmap (1-(dimethylamino)propan-2-olate), and dmop (2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)propan-2-olate) and their potential as precursors for MOCVD and ALD of CeO(2). New complexes were synthesized by alcohol exchange reactions with [Ce(OBu(t))(4)]. [Ce(mmp)(4)] and [Ce(dmap)(4)] were both found to be excellent precursors for liquid-injection MOCVD of CeO(2), depositing high purity thin films with very low carbon contamination, and both have a large temperature window for diffusion controlled growth (350-600 °C for [Ce(mmp)(4)]; 300-600 °C for [Ce(dmap)(4)]). [Ce(mmp)(4)] is also an excellent precursor for liquid-injection ALD of CeO(2) using H(2)O as oxygen source and demonstrates self-limiting growth from 150 to 350 °C. [Ce(dmap)(4)] has lower thermal stability than [Ce(mmp)(4)] and does not show self-limiting growth in ALD. Heteroleptic complexes show a tendency to undergo ligand redistribution reactions to form mixtures in solution and are unsuitable as precursors for liquid-injection CVD.

Precursors for MOCVD and ALD of rare earth oxides-complexes of the early lanthanides with a donor-functionalized alkoxide ligand.

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.

Samarium diiodide-catalyzed diastereoselective pinacol couplings.

A complex of samarium diiodide (SmI(2)) with tetraglyme catalyzes the intermolecular pinacol coupling of aromatic or aliphatic aldehydes at loadings of 10 mol % in the presence of Me(2)SiCl(2) and Mg. Diastereoselectivity of up to 95/5 (+/-/meso) has been achieved for aliphatic aldehydes and up to 19/81 (+/-/meso) for aromatic aldehydes. De values of up to 99% have been achieved in intramolecular pinacol coupling reactions using the SmI(2)/tetraglyme/Mg/Me(2)SiCl(2) catalytic system.

Alkali Metal Bis(o-anisyl)phosphides: Characterization of MP(C(6)H(4)OMe-o)(2) (M = Li, Na) and Crystal Structure of a Sodium Secondary Organophosphide.

Lithium bis(o-anisyl)phosphide (1)may be prepared by reaction of n-BuLi with bis(o-anisyl)phosphine in THF or toluene; sodium bis(o-anisyl)phosphide (2) is prepared by reaction of sodium with tris(o-anisyl)phosphine in liquid ammonia/THF; both compounds are isolated as unsolvated solids. 1 decomposes quantitatively in THF to give tetrakis(o-anisyl)diphosphine (4); 2 decomposes in THF to give a mixture containing 4 and bis(o-anisyl)phosphine. Addition of diglyme to 2 gives [Na{&mgr;-P(C(6)H(4)OMe-o)(2)}(MeO(CH(2)CH(2)O)(2)Me)](2) (2a), which has been characterized by single-crystal X-ray diffraction. Each Na atom in 2a is 6-coordinate, being bonded to two P atoms, three diglyme O atoms, and one O atom from an o-anisyl group. Crystal data: monoclinic, P2(1)/n, a = 14.549(4) Å, b = 18.555(6) Å, c = 15.846(4) Å, beta = 91.07(2) degrees, Z = 4, final R = 0.041, R(w) = 0.053.