300. The amino-derivatives of pentaerythritol. Part I. Preparation

A. MCAULEY, K . BEVERIDGE, S. SUBRAMANIAN, and T. W. WHITCOMBE. Can. J . Chem. 67, 1657Chem. 67, (1989. Reaction of pentaerythrityltetrabromide with ethylenediamine yields three product amines. These have been isolated by separation of the corresponding Ni2+ complexes. The free amine hydrochlorides have been obtained by acid hydrolysis of the ~i~+ species and have been characterized by nuclear magnetic resonance and mass spectroscopy.

Section: Crystal Structurescontrasting

confidence: 47%

Section: Introductionmentioning

confidence: 99%

Isolation and characterization of polydentate ligands derived from the reaction of pentaerythrityltetrabromide and ethylenediamine

McAuley¹,

Beveridge²,

Subramanian³

et al. 1989

“…There are only two relevant methods for the preparation of tam available in the literature (1,15). The drastic experimental conditions and the tedious nature of the preparatory method of Litherland and Mann (1) often yield products of poor quality even though it is the reasonable method for the preparation of substantial amounts of the tetratosylate.…”

Section: Results and Discussion Preparation Of Ligandsmentioning

confidence: 99%

Synthesis and crystal structure of an octahedral nickel(II) complex derived from pentaerythrityl tetraamine

McAuley¹,

Subramanian²,

Whitcombe³

1989

A. MCAULEY, S. SUBRAMANIAN, and T. W. WHITCOMBE. Can. J. Chem. 67, 1650 (1989). The Ni(I1) complex, ~i ( H t a m )~~+ (tam = pentaerythrityl tetraamine), has been prepared under controlled conditions. In this ion, three of the four amino groups of each ligand are coordinated to yield an octahedral structure which shows tetragonal and trigonal distortion. The fourth amino group is protonated in each case and binds strongly to the counter ion so4*-. The crystal structure (triclinic, P i , a = 8.913(3), b = 9.775(2), c = 7.505(3), a = 102.61(4)", P = 106.28(4)", y = 96.40(3)") has been refined, converging to final values ofR = 0.0347 and R,,, = 0.0386. The three dimensional nature of the hydrogen bonding in the crystal structure has been described. Differences in Ni-N bond lengths are observed. A transient nickel(II1) species is generated chemically or electrochemically. The esr spectrum is consistent with a low spin d7 centre and is axial in nature.Key words: nickel, pentaerythrityl tetraamine, hydrogen bonding, oxidation.A. MCAULEY, S. SUBRAMANIAN et T. W. WHITCOMBE. Can. J. Chem. 67, 1650 (1989). Optrant dans des conditions contr61ies, on a pripari le complexe de Ni(II), N i ( H t a~n )~~+ (tam = pentatrythrityl tttraamine). Dans cet ion, trois des quatre groupements amints de chacun des ligands sont coordonnis pour donner une structure octaedrique qui prtsente une distorsion tttragonale et trigonale. Dans chaque cas, le quatritme-groupement amini est protone et il se lie fortement au contre-ion ~0 4~' .On a affini la structure cristalline (triclinique, PI, a = 8,913(3), b = 9,775(2) et c = 7,505(3) A, a = 102,61(4), P = 106,28(4) et y = 96,40(3)") jusqu'i des valeurs finales de R = 0,0347 et R,,. = 0,0386. On decrit la nature tridimensionnelle des liaisons hydrogenes dans la structure cristalline. On a observt des differences dans les longueurs des liaisons Ni-N. I1 y a gkniration chimique ou Clectrochimique d'une espece transitoire de Ni(II1). Le spectre rpe est en accord avec un centre d7 de faible spin et de nature exiale.

“…25, the chloride appears to remain unaffected up to 300°C when heated rapidly; on slow hcating it decomposes above ca. 260°C.…”

Section: Methodsmentioning

confidence: 99%

“…The sulfate is only slightly soluble in water, but it dissolves In concentrated sulfuric acid (25). In an early attempt to obtain crystals 'TO whom all correspondence may be addressed.…”

Section: Methodsmentioning

confidence: 99%

Crystal structures of tetrakis(ammoniomethyl)methane tetrachloride, C(CH₂NH₃)₄Cl₄, and disulfate, C(CH₂NH₃)₄(SO₄)₂

Cameron¹,

Chute²,

Knop³

1985

The crystal structures of C(CH2NH3)4Cl4 (P42/n, a = 9.503(1) Å, c = 6.549(1) Å, Z = 2) and C(CH2NH3)4(SO4)2 (P212121, a = 8.382(2) Å, b = 10.508(3) Å, c = 14.400(3) Å, Z = 4) have been determined. Both crystals contain strong [Formula: see text] bonds; in the sulfate the hydrogen-bonding network is particularly extensive. The thermal motion of the cation can be described satisfactorily as a rigid-body motion.