Synthesis of complexes of 2,2 ': 6 ',2 ''-terpyridine and 1,10-phenanthroline with lanthanide thiocyanates; the molecular structures of [Ln(terpy)(2)(NCS)(3)] (Ln = Pr, Nd), [Nd(terpy)(2)(NCS)(3)]center dot 2EtOH and [Ln(phen)(3)(NCS)(3)]center dot EtOH (Ln = Pr, Nd)

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https://doi.org/10.1016/S0277-5387(03)00133-5
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Keywords

2,2 ': 6 ',2 ''-terpyridine, 1,10-phenanthroline, praseodymium, 2,2'/6',2-TERPYRIDINE, LIGANDS, CRYSTAL-STRUCTURES, COORDINATION, X-RAY, HYDRATED 1/1-ADDUCTS, X-ray crystal structures, SYSTEMATICS, NITRATE, RARE-EARTH COMPLEXES, neodymium

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Synthesis of complexes of 2,2 ': 6 ',2 ''-terpyridine and 1,10-phenanthroline with lanthanide thiocyanates; the molecular structures of [Ln(terpy)(2)(NCS)(3)] (Ln = Pr, Nd), [Nd(terpy)(2)(NCS)(3)]center dot 2EtOH and [Ln(phen)(3)(NCS)(3)]center dot EtOH (Ln = Pr, Nd). / Cotton, Simon A.; Franckevicius, Vilius; How, Rachel E. et al.
In: Polyhedron, Vol. 22, No. 11, 01.06.2003, p. 1489-1497.

Research output: Contribution to Journal/Magazine › Journal article › peer-review

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@article{b6c9e3ea1a5e48adb58f726ea3c788e1,

title = "Synthesis of complexes of 2,2 ': 6 ',2 ''-terpyridine and 1,10-phenanthroline with lanthanide thiocyanates; the molecular structures of [Ln(terpy)(2)(NCS)(3)] (Ln = Pr, Nd), [Nd(terpy)(2)(NCS)(3)]center dot 2EtOH and [Ln(phen)(3)(NCS)(3)]center dot EtOH (Ln = Pr, Nd)",

abstract = "The complexes [Ln(terpy)(2)(NCS)(3)] (Ln = Pr (1), Nd (2); terpy = 2,2':6',2{"}-terpyridine), [Nd(terpY)2(NCS)(3)]-2EtOH (3) and [Ln(phen)3(NCS)3].EtOH (Ln = Pr(4), Nd (5); phen = 1,10-phenanthroline) have been synthesised in high yield by the reaction of [Ln(NO3)(3)].6H(2)O (Ln = Pr, Nd) with KNCS and subsequently with terpy or phen, respectively. The five complexes have been characterised crystallographically, and it is found that the pairs of complexes, I and 2, and 4 and 5 are isomorphous with each other. In all the complexes the lanthanoid ions are nine co-ordinate, and all contain meridionally disposed thiocyanate groups. The molecular geometry of 3 is very similar to that of 2, and the crystal structure differs only in the presence of the two ethanol solvent molecules. In the whole series of complexes the Ln-N(thiocyanate) distances are shorter than the Ln-N(terpy/phen) distances and there is a shortening of all the lanthanoid-ligand bonds in the neodymium complexes compared with the praseodymium, consistent with the expected 'lanthanide contraction' that occurs as additional electrons enter the 4f orbitals. In all the complexes the thiocyanate groups are linear, but there is a significant variation in the angle at the thiocyanate at nitrogen and Ln-N-C angles lie in the range 147-177degrees. (C) 2003 Elsevier Science Ltd. All rights reserved.",

keywords = "2,2 ': 6 ',2 ''-terpyridine, 1,10-phenanthroline, praseodymium, 2,2'/6',2-TERPYRIDINE, LIGANDS, CRYSTAL-STRUCTURES, COORDINATION, X-RAY, HYDRATED 1/1-ADDUCTS, X-ray crystal structures, SYSTEMATICS, NITRATE, RARE-EARTH COMPLEXES, neodymium",

author = "Cotton, {Simon A.} and Vilius Franckevicius and How, {Rachel E.} and Birte Ahrens and Ooi, {Li Ling} and Mahon, {Mary F.} and Raithby, {Paul R.} and Teat, {Simon J.}",

year = "2003",

month = jun,

day = "1",

doi = "10.1016/S0277-5387(03)00133-5",

language = "English",

volume = "22",

pages = "1489--1497",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Limited",

number = "11",

}

RIS

TY - JOUR

T1 - Synthesis of complexes of 2,2 ': 6 ',2 ''-terpyridine and 1,10-phenanthroline with lanthanide thiocyanates; the molecular structures of [Ln(terpy)(2)(NCS)(3)] (Ln = Pr, Nd), [Nd(terpy)(2)(NCS)(3)]center dot 2EtOH and [Ln(phen)(3)(NCS)(3)]center dot EtOH (Ln = Pr, Nd)

AU - Cotton, Simon A.

AU - Franckevicius, Vilius

AU - How, Rachel E.

AU - Ahrens, Birte

AU - Ooi, Li Ling

AU - Mahon, Mary F.

AU - Raithby, Paul R.

AU - Teat, Simon J.

PY - 2003/6/1

Y1 - 2003/6/1

N2 - The complexes [Ln(terpy)(2)(NCS)(3)] (Ln = Pr (1), Nd (2); terpy = 2,2':6',2"-terpyridine), [Nd(terpY)2(NCS)(3)]-2EtOH (3) and [Ln(phen)3(NCS)3].EtOH (Ln = Pr(4), Nd (5); phen = 1,10-phenanthroline) have been synthesised in high yield by the reaction of [Ln(NO3)(3)].6H(2)O (Ln = Pr, Nd) with KNCS and subsequently with terpy or phen, respectively. The five complexes have been characterised crystallographically, and it is found that the pairs of complexes, I and 2, and 4 and 5 are isomorphous with each other. In all the complexes the lanthanoid ions are nine co-ordinate, and all contain meridionally disposed thiocyanate groups. The molecular geometry of 3 is very similar to that of 2, and the crystal structure differs only in the presence of the two ethanol solvent molecules. In the whole series of complexes the Ln-N(thiocyanate) distances are shorter than the Ln-N(terpy/phen) distances and there is a shortening of all the lanthanoid-ligand bonds in the neodymium complexes compared with the praseodymium, consistent with the expected 'lanthanide contraction' that occurs as additional electrons enter the 4f orbitals. In all the complexes the thiocyanate groups are linear, but there is a significant variation in the angle at the thiocyanate at nitrogen and Ln-N-C angles lie in the range 147-177degrees. (C) 2003 Elsevier Science Ltd. All rights reserved.

AB - The complexes [Ln(terpy)(2)(NCS)(3)] (Ln = Pr (1), Nd (2); terpy = 2,2':6',2"-terpyridine), [Nd(terpY)2(NCS)(3)]-2EtOH (3) and [Ln(phen)3(NCS)3].EtOH (Ln = Pr(4), Nd (5); phen = 1,10-phenanthroline) have been synthesised in high yield by the reaction of [Ln(NO3)(3)].6H(2)O (Ln = Pr, Nd) with KNCS and subsequently with terpy or phen, respectively. The five complexes have been characterised crystallographically, and it is found that the pairs of complexes, I and 2, and 4 and 5 are isomorphous with each other. In all the complexes the lanthanoid ions are nine co-ordinate, and all contain meridionally disposed thiocyanate groups. The molecular geometry of 3 is very similar to that of 2, and the crystal structure differs only in the presence of the two ethanol solvent molecules. In the whole series of complexes the Ln-N(thiocyanate) distances are shorter than the Ln-N(terpy/phen) distances and there is a shortening of all the lanthanoid-ligand bonds in the neodymium complexes compared with the praseodymium, consistent with the expected 'lanthanide contraction' that occurs as additional electrons enter the 4f orbitals. In all the complexes the thiocyanate groups are linear, but there is a significant variation in the angle at the thiocyanate at nitrogen and Ln-N-C angles lie in the range 147-177degrees. (C) 2003 Elsevier Science Ltd. All rights reserved.

KW - 2,2 ': 6 ',2 ''-terpyridine

KW - 1,10-phenanthroline

KW - praseodymium

KW - 2,2'/6',2-TERPYRIDINE

KW - LIGANDS

KW - CRYSTAL-STRUCTURES

KW - COORDINATION

KW - X-RAY

KW - HYDRATED 1/1-ADDUCTS

KW - X-ray crystal structures

KW - SYSTEMATICS

KW - NITRATE

KW - RARE-EARTH COMPLEXES

KW - neodymium

U2 - 10.1016/S0277-5387(03)00133-5

DO - 10.1016/S0277-5387(03)00133-5

M3 - Journal article

VL - 22

SP - 1489

EP - 1497

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

IS - 11

ER -

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