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, Olivier Cador 3 and Grégory Nocton. 1 *

C. Lcm and E. Polytechnique,

, CNRS, ISCR, vol.6226

U. Lyon and . Lyon, , p.69342

, ) Å. These distances are dictated by the crown-ether chelate

, 26 Since there is no available data on thulium crown-ether complexes in the literature, the only possible comparison is with ytterbium derivatives featuring similar ionic radius: in Yb(NPh2)2(18-c-6), 35 the Yb II -O

, H(BH4) distance is 2.4(1) Å. These distances fit well with the Tm-B distances observed by Nief in Tm(BH4)2(dme)2 that range between 2.632(4) Å and 2.656(5) Å and the Tm-H

, 655 Å) and Tm-H(BH4) (between 2.459 Å and 2.551 Å) distances are observed on the Tp'Tm(BH4) complex

, 14 Å) but the Tm-B distance remain similar (2.631 Å). 38 In this particular case, the steric influence of the bulky Cp ttt ligands 40 can explain this long Tm-B distance. Indeed, a homoleptic Tm(BH4) -thulium complexes, in which the equatorial ligand field is dominant, a failed and further work is in progress in this direction, the Tm-H(BH4) distances are much shorter

, (1156 nm) and 8561 cm -1 (1168 nm) are observed, vol.8909, pp.8649-8650, 1133.

, As important conclusions from the analysis of this spectrum, (i) the overall crystal field splitting is rather small (263 cm -1 ) and (ii) the ground mJ state is close to the first excited one References 1

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. Tm, O(2A) 2.639(5) Tm(1)-O(1B)

, C(5B)-H(5C)

C. ,

C. ,

C. ,

C. ,

, C(5A)-H(5A)

. O(2a)-tm, O(1B)#2 142.8(2) O(1B)-Tm(1)-O(3B), vol.119

. O(1b)#2-tm,

. O(2a)-tm, , p.2

. O(2a)-tm,

. O(1a)-tm,

. O(2a)-tm, , p.2

. O(3a)-tm, , p.2

. O(1b)#2-tm,

. O(3b)-tm,

, O(3B)#2-Tm(1)-O(2B)

, O(2A)-Tm(1)-I(2) 92.4(1)

, O(1B)-Tm(1)-I(2) 92.5(1)

, O(1B)#2-Tm(1)-I(2) 87.5(1)

, O(3B)-Tm(1)-I(2) 84.0(1)

, O(3B)#2-Tm(1)-I(2) 96.0(1)

, O(1A)-Tm(1)-I(2) 91.2(1)

, O(3A)-Tm(1)-I(2)

, O(2B)-Tm(1)-I(2) 91.2(1)

, O(2A)-Tm(1)-I(2)#2, vol.87

. O(1a)-tm, , p.2

, Tm(1)-I, p.2

, C(2)-O(1B)-Tm(1)

, C(2)-O(2A)-C(5A)

O. , C(5B) 105.9(4) O(2A)-C(2)-C(1A)

, C(5B)-C(2)-H(2A)

C. ,

. H(2a,

, O(3B)-C(3)-H(3A)

, C(6)-C(4B)-O(3B)

, O(2B)-C(5B)-C(2) 107.2(5)

, C(5B)-H(5C), vol.110

, C(5B)-H(5D), vol.110

, O(2B)-C(6)-C(4B) 116.3(5)

. O(3a, C(6)-C(5A) 96.5(4)

, O(2B)-C(6)-H(6A)

, O(2B)-C(6)-H(6B)

. H(6a,

, O(1A)-C(1A)-C(2) 106.7(5) O(1A)-C(1A)-H(1A)

C. , C(4A)-H(4B), vol.109

. O(2a, C(5A)-C(6) 102.2(5) O(2A)-C(5A)-H(5A)

S. Table, Bond lengths (Å) and angles (°) for TmI

. Tm, , p.10

B. , , p.12

B. , , p.3

, B(1)-Tm(1)-O(1)#10 88.4(1)

. #12-tm, )#10 119.93(1) O(1)#3-Tm, p.10

B. , , p.11

. #3-tm, O(1)#11 60.08(1) O(1)#10-Tm, p.11

B. , , p.2

, B(1)-Tm(1)-I(1), p.10

. #12-tm, )-I(1)#10 88.4(1) O(1)#3-Tm(1)-I, p.10

, O(1)#2-Tm(1)-I(1), p.10

, B(1)#10-Tm(1)-H(2B1)

, O(1)#12-Tm(1)-H(2B1)

. #3-tm, H(2B1) 103(3) O(1)#10-Tm(1)-H(2B1), vol.114

, Tm(1)-H(2B1), ) O(1)#11-Tm(1)-H(2B1), vol.65

I. , Tm(1)-H(2B1) 154.3(1)

. #10-tm,

, B(1)#10-I(1)-Tm(1)

, I(1)#10-B(1)-H(1B1)

, I(1)#10-B(1)-H(2B1)

, H(1B1)-B(1)-H(2B1)

, C(2)#12-C(1)-H(1A)

, C(2)#12-C(1)-H(1B)

, C(1)#11-C(2)-H(2A)

, C(1)#11-C(2)-H(2B)

, C(11)-H(11A)

, C(12)-H(12A)

, C(12)-H(12C)

, H(100)-Tm(1)-H(101)

, H(100)-Tm(1)-H(103)

, H(1A)-C(1)-H(1B)

, H(1A)-C(1)-H(1C)

, C(3)-C(2)-H(2A)

C. ,

. H(2a,

, C(3)-H(3A)

, C(3)-H(3B)

, C(4)-H(4A)

, O(3)-C(5)-H(5A)

, H(5A)-C(5)-H(5B)

, H(5A)-C(5)-H(5C)

C. , C(6)-H(6A)

C. , C(6)-H(6B)

C. ,

C. ,

, O(4)-C(8)-H(8A)

, H(8A)-C(8)-H(8B)

, H(8A)-C(8)-H(8C)

, H(9A)-C(9)-H(9B)

, H(9A)-C(9)-H(9C)

, C(11)-C(10)-H(10A)

C. ,

H. ,

C. , C(11)-H(11A)

C. ,

H. ,

, C(12)-H(12A)

, H(12A)-C(12)-H(12B)

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