Synthesis of germylcopper compounds by hydride method. Crystal structure of (C6F5)3GeCu(PPh3)2

Article abstract of DOI:10.1016/S0022-328X(98)00389-1

Germylcopper compounds Ph₃GeCu(PPh₃)₃ (1) and (C₆F₅)₃GeCu(PPh₃)₂ (2) were synthesized by reaction of organogermanium hydrides R₃GeH (R=Ph, C₆F₅) with t-BuOCu in the presence of PPh₃. The crystal structure of 2 and its analogous {(C₆F₅)₃GeCu(PPh₃)₂}(THF) ₂ (3) with two additional solvate THF molecules have been determined by X-ray diffraction method. In both 2 and 3 crystals the Cu atom is bonded to the Ge atom of (C₆F₅)₃Ge group and the two P atoms of PPh₃ ligands and have a slightly distorted planar-trigonal environments. The Cu-Ge distances are 2.370(2), 2.382(2) A in 2 (for two independent molecules) and 2.348(1) A in 3.

Full text of DOI:10.1016/S0022-328X(98)00389-1

Journal of Organometallic Chemistry 560 (1998) 21–25
Synthesis of germylcopper compounds by hydride method. Crystal
structure of (C6F5)3GeCu(PPh3)2
Nikolay A. Orlov a, Leonid N. Bochkarev a,*, Alexander V. Nikitinsky a,
Valentina Yu. Kropotova a, Lev N. Zakharov b, Georgy K. Fukin b, Stanislav Ya. Khorshev b
a Department of Chemistry, Nizhny No6gorod State Pedagogical Uni6ersity, Ulyano6a 1, Nizhny No6gorod, 603600, Russia
b Institute of Organometallic Chemistry, Russian Academy of Sciences, Tropinina 49, Nizhny No6gorod, 603600, Russia
Received 4 July 1997; received in revised form 18 December 1997
Abstract
Germylcopper compounds Ph3GeCu(PPh3)3 (1) and (C6F5)3GeCu(PPh3)2 (2) were synthesized by reaction of organogermanium
hydrides R3GeH (R=Ph, C6F5) with t-BuOCu in the presence of PPh3. The crystal structure of 2 and its analogous
{(C6F5)3GeCu(PPh3)2}(THF)2 (3) with two additional solvate THF molecules have been determined by X-ray diffraction method.
In both 2 and 3 crystals the Cu atom is bonded to the Ge atom of (C6F5)3Ge group and the two P atoms of PPh3 ligands and
˚
have a slightly distorted planar-trigonal environments. The Cu–Ge distances are 2.370(2), 2.382(2) A in 2 (for two independent
˚
molecules) and 2.348(1) A in 3. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Germanium; Copper; Hydride method; X-ray diffraction
1. Introduction
2. Results and discussion
Organocopper compounds and organocuprates are
well known and widely used in organic synthesis [1].
Organometallic analogs with copper–silicon [2] and
copper–germanium bonds [3,4] are rare and not much
known about their chemical behavior. Nevertheless
such type of organocopper derivatives might be ex-
pected as promising reagents in organometallic synthe-
sis. Reported synthetic route to organogermanium
derivatives of copper consists of metal–halogen ex-
change reaction [3]. This method allowed to obtain the
germylcopper compounds only in very low yield and
they are rather difficult to purify from lithium chloride
as a side product. Here we report that the titled com-
pounds can be synthesized in high yields and without
additional purification by hydride method which is
known to be a convenient synthetic pathway to bi- and
polyelement organometallic compounds [5].
Organogermanium hydrides R3GeH (R=Ph, C6F5)
were found to react with t-BuOCu in DME at 50°C
and form organogermanium derivatives of copper 1
and 2 in 83.8–92.0% yield.
DME
R3GeH+t-BuOCu+nPPh3 5“0°C 1(2)+nt-BuOH
R=Ph, n=3; R=C6F5, n=2
Complex 1 was isolated as colorless unstable in air
crystalline solid which according elemental analysis, m.
pt. and IR data is identical to germylcopper compound
originally obtained by the reaction of Ph3GeLi with
CuCl [3]. The novel compound 2 was isolated as stable
in air colorless crystals soluble in THF, DME, spar-
ingly soluble in benzene, insoluble in hexane. It melts
with decomposition at 212–214°C. IR spectrum shows
the absorption bands of (C6F5)3Ge fragment and of
coordinated PPh3 ligands. The THF solvate compound
3 was isolated after recrystallization of 2 from THF.
* Corresponding author.
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00389-1

22
N.A. Orlo6 et al. / Journal of Organometallic Chemistry 560 (1998) 21–25
Fig. 1. The general view of the (C6F5)3GeCu(PPh3)2 in 3 and atom labeling.
The crystal structure of 2 and its analogous 3 with
spectively. The average C–F, C–C distances of
(C6F5)3Ge groups and the C–C distances of PPh3 lig-
ands are 1.35(1), 1.38(2) and 1.38(2) A in 2 (the average
two additional solvate THF molecules have been deter-
mined by X-ray diffraction method. In both crystals the
(C6F5)3GeCu(PPh3)2 molecule have a similar structure.
The Cu atom is bonded to the Ge atom of (C6F5)3Ge
group and the two P atoms of PPh3 ligands and have a
slightly distorted planar-trigonal environments (Fig. 1).
Sums of the bond angles at the Cu atoms are 360.0°
(359.8°) in 2 (here and below the values for second
symmetrically independent molecule in 2 are given in
parenthesis) and 359.9° in 3 and the values of these
angles are in the ranges 117.2(1)–123.1(1)° (115.0(1)–
123.1(1)°) in 2 and 116.7(1)–122.0(1)° in 3 (Table 1).
The Cu–Ge distances 2.382(2), 2.370(2) and 2.348(1)
˚
values for two independent molecules); 1.35(1), 1.37(2)
˚
and 1.38(2) A in 3.
3. Experimental section
3.1. Preparation of 1 and 2
The synthesis and isolation of 1 and 2 were per-
formed under vacuum in sealed ampoules using thor-
oughly dried solvents. The IR spectra were recorded on
a Perkin–Elmer-577 spectrometer.
˚
A found in neutral 2 and 3 are slightly longer then
those in anion [(Ph3Ge)2Cu]− 2.339 and 2.336 A [4].
˚
The Cu(1)–P(1), Cu(1)–P(2) distances are 2.269(3),
3.1.1. Preparation of 1
˚
˚
2.256(3) A (2.272(3), 2.274(3) A) in 2 and 2.255(3),
A mixture of Ph3GeH (3.80 g, 12.5 mmol), t-BuOCu
(1.68 g, 12.3 mmol) and PPh3 (9.75 g, 37.2 mmol) in 40
ml of DME was heated to 50°C for ca. 2 h. The solvent
and volatile products were removed from the reaction
solution and the residue was washed with hexane (3×
15 ml), dried in vacuum to yield 13.06 g, (92.0%) of 1,
m. pt: (dec.) 132–134°C. Anal. Calcd. for C72Cu1H60
Ge1P3: C, 74.93; Cu, 5.50; H, 5.20. Found: C, 74.40;
Cu, 5.71; H,5.95. IR (Nujol, cm−1): (Ph–Ge) 3040,
1480, 1425, 1085, 1065, 1020, 995, 730, 690, 460; (coor-
dinated PPh3) 3040, 1420, 1090, 1020, 740, 685, 500. In
volatile products 0.77 g (84.6%) of t-BuOH was found.
˚
2.248(3) A in 3. Some differences between the similar
bond lengths found in 2 and 3 seem to be related with
differences of crystal packing in these compounds.
The Ge and P atoms of the (C6F5)3Ge groups and
PPh3 ligands in 2 and 3 have a distorted tetrahedral
coordination (Table 1). The Ge–C and P–C distances
˚
are in the ranges: 1.994(9)–2.028(7)
A
(average
(average
˚
˚
2.013(21) A) and 1.811(7)–1.845(9)
A
˚
1.825(12) A) in 2 (for two independent molecules);
˚
˚
˚
1.998(9)–2.025(9)
A
(average 2.008(13) A) and
˚
1.806(9)–1.840(10) A (average 1.827(12) A) in 3, re-

N.A. Orlo6 et al. / Journal of Organometallic Chemistry 560 (1998) 21–25
23
Table 1
Selected bond lengths (A) and bond angles (°) in 2 and 3
˚
Table 2
Atomic coordinates (×l04) and equivalent isotropic displacement
coefficients (A ×10 ) for 2
2
3
˚
2, molecule A 2, molecule B
3
Bond lengths
Cu(1)–Ge(1)
Cu(1)–P(1)
Cu(1)–P(2)
Ge(1)–C(1)
Ge(1)–C(7)
Ge(1)–C(13)
P(1)–C(19)
P(1)–C(25)
P(1)–C(31)
P(2)–C(37)
P(2)–C(43)
P(2)–C(49)
x
y
z
Ueq
2.370(2)
2.269(3)
2.256(3)
2.000(7)
2.028(7)
2.016(8)
1.818(9)
1.841(7)
1.822(8)
1.825(8)
1.829(8)
1.811(7)
2.382(2)
2.272(3)
2.274(3)
1.994(9)
2.014(8)
2.017(8)
1.826(10)
1.816(9)
1.835(8)
1.825(9)
1.845(9)
1.827(10)
2.348(1)
2.255(3)
2.248(3)
1.988(9)
2.025(9)
2.003(9)
1.820(10)
1.823(9)
1.839(10)
1.840(10)
1.823(9)
1.806(9)
Cu(1A)
Ge(1A)
P(1A)
P(2A)
F(2A)
F(3A)
F(4A)
F(5A)
F(6A)
4385(1)
5974(1)
3232(2)
4076(2)
6175(5)
7828(6)
9723(5)
9922(4)
8296(4)
4413(4)
3710(4)
4649(5)
6231(5)
6907(4)
7244(4)
8284(4)
8358(4)
7485(4)
6502(4)
7169(6)
7106(7)
7934(9)
8884(9)
8999(7)
8142(6)
5701(6)
4881(7)
4521(7)
4962(8)
5783(8)
6125(7)
6799(6)
7291(6)
7833(7)
7881(6)
7417(6)
6911(6)
3557(6)
4469(7)
4794(9)
4224(11)
3327(10)
3005(8)
1957(6)
1959(8)
1063(9)
131(8)
5591(1)
5105(1)
5116(1)
6483(1)
6101(3)
6586(4)
6131(4)
5177(4)
4696(3)
4129(3)
2776(3)
1949(3)
2521(3)
3869(3)
6430(2)
6799(3)
5851(4)
4531(3)
4134(3)
5375(4)
5861(5)
6112(5)
5877(6)
5396(5)
5159(4)
4054(4)
3737(4)
3048(5)
2638(5)
2920(5)
3625(4)
5289(4)
5928(4)
6141(5)
5681(5)
4997(5)
4808(5)
4349(4)
4428(5)
3882(6)
3246(6)
3148(5)
3698(5)
4841(4)
4459(6)
4271(7)
4456(6)
4848(5)
5026(4)
5698(4)
6393(5)
6856(5)
6597(6)
5911(6)
5445(5)
6578(4)
6003(4)
6052(5)
6667(5)
7246(5)
7208(4)
6575(4)
7545(1)
7632(1)
8071(1)
6948(1)
9061(3)
34(1)
35(1)
38(1)
36(1)
80(3)
126(4)
125(4)
98(3)
63(2)
62(2)
84(3)
93(3)
87(3)
64(2)
59(2)
77(3)
89(3)
83(3)
64(2)
39(3)
53(4)
68(4)
78(5)
62(4)
45(3)
37(3)
45(3)
60(4)
59(4)
59(4)
47(3)
38(3)
38(3)
52(4)
55(4)
55(4)
44(3)
44(3)
65(4)
73(5)
85(6)
81(5)
66(4)
43(3)
80(5)
98(6)
75(5)
66(4)
48(3)
41(3)
52(4)
71(5)
67(4)
61(4)
56(4)
33(3)
45(3)
55(4)
59(4)
65(4)
48(3)
42(3)
10 149(3)
10 178(3)
9113(3)
8009(3)
6483(3)
6283(3)
7191(3)
8320(3)
8549(3)
7519(3)
6609(3)
5478(3)
5328(3)
6262(3)
8490(4)
9064(5)
9622(5)
9642(5)
9093(5)
8540(4)
7510(4)
6951(4)
6836(5)
7294(5)
7857(5)
7965(4)
6937(4)
6978(4)
6521(5)
5963(5)
5868(4)
6363(4)
8459(4)
8996(5)
9332(5)
9111(7)
8579(6)
8244(5)
7434(4)
6790(5)
6285(6)
6376(6)
7005(5)
7530(4)
8789(4)
8892(4)
9416(5)
9877(5)
9794(4)
9255(4)
6322(4)
5830(4)
5298(4)
5258(5)
5759(5)
6287(4)
6434(4)
F(8A)
F(9A)
F(1OA)
F(11A)
F(12A)
F(14A)
F(15A)
F(16A)
F(17A)
F(18A)
C(1A)
C(2A)
C(3A)
C(4A)
C(5A)
Bond angles
Ge(1)–Cu(1)–P(1)
Ge(1)–Cu(1)–P(2)
P(1)–Cu(1)–P(2)
Cu(1)–Ge(1)–C(1)
Cu(1)–Ge(1)–C(7)
117.2(1)
115.0(1)
116.7(1)
122.0(1)
121.2(1)
115.4(2)
112.6(2)
121.1(3)
104.6(4)
96.8(4)
104.1(4)
117.5(3)
110.0(3)
102.6(4)
114.8(3)
103.9(4)
106.9(4)
114.5(3)
111.7(3)
104.8(4)
117.1(3)
117.1(3)
104.6(4)
119.7(1)
123.1(1)
121.5(2)
109.8(2)
121.7(1)
123.1(1)
122.8(3)
120.6(2)
95.1(3)
Cu(1)–Ge(1)–C(13) 118.0(2)
C(1)–Ge(1)–C(7)
C(1)–Ge(1)–C(13)
C(7)–Ge(1)–C(13)
Cu(1)–P(1)–C(19)
Cu(1)–P(1)–C(25)
C(19)–P(1)–C(25)
Cu(1)–P(1)–C(31)
C(19}–P(1)–C(31)
C(25)–P(1)–C(31)
Cu(1)–P(2)–C(37)
Cu(1)–P(2)–C(43)
C(37)–P(2)–C(43)
Cu(1)–P(2)–C(49)
C(37)–P(2)–C(49)
C(43)–P(2)–C(49)
104.8(3)
95.7(3)
108.4(3)
103.9(3)
103.3(4)
116.1(3)
111.5(3)
105.9(4)
116.7(3)
101.7(4)
103.5(4)
113.2(3)
121.7(2)
102.4(4)
110.0(3)
104.0(4)
103.8(4)
105.1(3)
117.1(3)
110.7(3)
104.6(4)
115.1(3)
103.3(4)
104.8(4)
115.0(3)
121.7(3)
102.4(4)
105.3(3)
107.1(4)
104.2(4)
C(6A)
C(7A)
C(8A)
C(9A)
C(10A)
C(11A)
C(12A)
C(13A)
C(14A)
C(15A)
C(16A)
C(17A)
C(18A)
C(19A)
C(20A)
C(21A)
C(22A)
C(23A)
C(24A)
C(25A)
C(26A)
C(27A)
C(28A)
C(29A)
C(30A)
C(31A)
C(32A)
C(33A)
C(34A)
C(35A)
C(36A)
C(37A)
C(38A)
C(39A)
C(40A)
C(41A)
C(42A)
C(43A)
3.1.2. Preparation of 2
A mixture of (C6F5)3GeH (1.94 g, 3.38 mmol), t-
BuOCu (0.46 g, 3.37 mmol) and PPh3 (1.77 g, 6.76
mmol) in 20 ml of DME was heated to 50°C for ca. 4
h. The solvent and volatile products were removed
from the reaction solution and the residue was washed
with hexane (3x15 ml), dried in vacuum to yield 3.28 g,
(83.8%) of 2, m. pt: (dec.) 212–214°C. Anal. Calcd for
C54Cu1H30Ge1F15P2: C, 55.82; Cu, 5.65; H, 2.60.
Found: C, 55.53; Cu, 5.15; H, 2.81. IR (Nujol, cm−1):
(C6F5-Ge) 1640, 1500, 1490, 1370, 1260, 1070, 960, 770,
605 (coordinated PPh3) 3040, 1420, 1090, 1020, 740,
685, 500. In volatile products 0.20 g (80.0%) of t-BuOH
was found.
124(7)
1024(6)
2957(6)
3294(7)
3083(8)
2563(8)
2244(7)
2441(7)
4857(5)
4845(6)
5334(7)
5872(7)
5920(7)
5401(6)
2769(6)
The crystalline samples of unsolvated 2 suitable for
X-ray analysis were obtained by crystallization of the
compound from benzene–hexane mixture. The crystals
of THF-solvate 3 for X-ray study were isolated after
recrystallization of 2 from THF.

24
N.A. Orlo6 et al. / Journal of Organometallic Chemistry 560 (1998) 21–25
Table 2 (continued)
Table 2 (continued)
x
y
z
Ueq
x
y
z
Ueq
C(33B)
C(34B)
C(35B)
C(36B)
C(37B)
C(38B)
C(39B)
C(40B)
C(41B)
C(42B)
C(43B)
C(44B)
C(45B)
C(46B)
C(47B)
C(48B)
C(49B)
C(50B)
C(51B)
C(52B)
C(53B)
C(54B)
7875(9)
7811(9)
8624(8)
9518(8)
8535(6)
9128(7)
9651(6)
9567(5)
10 261(4)
10 137(5)
10 532(6)
11 061(7)
11 181(6)
10 777(5)
8888(4)
8278(4)
7659(5)
7657(5)
8253(5)
8870(5)
10 065(5)
9818(6)
10 110(7)
10 631(7)
10 885(5)
10 588(5)
10 347(6)
10 045(5)
10 244(5)
10 730(5)
14 378(4)
14 634(5)
15 275(5)
15 618(5)
15 362(6)
14 737(5)
13 869(4)
13 384(5)
13 602(6)
14 311(5)
14 790(6)
14 573(5)
13 369(4)
13 560(5)
13 392(7)
13 022(7)
12 814(6)
12 989(5)
83(5)
81(5)
70(4)
60(4)
47(3)
58(4)
79(5)
88(6)
83(5)
60(4)
41(3)
59(4)
72(5)
65(4)
69(5)
56(4)
52(4)
71(5)
94(6)
90(6)
78(5)
65(4)
C(44A)
C(45A)
C(46A)
C(47A)
C(48A)
C(49A)
C(50A)
C(51A)
C(52A)
C(53A)
C(54A)
Cu(1B)
Ge(1B)
P(1B)
P(2B)
F(2B)
F(3B)
F(4B)
F(5B)
F(6B)
F(8B)
F(9B)
F(1OB)
F(11B)
F(12B)
F(14B)
F(15B)
F(16B)
F(17B)
F(18B)
C(1B)
C(2B)
C(3B)
C(4B)
C(5B)
1915(8)
931(8)
771(8)
1596(9)
2597(7)
4422(6)
3715(6)
3970(8)
4945(9)
6342(6)
6387(6)
6659(5)
6906(6)
6863(5)
7259(4)
7717(4)
8249(5)
8339(6)
7902(6)
7360(5)
9730(1)
6632(6)
6260(7)
5660(6)
5445(6)
5823(5)
7614(4)
7745(5)
8328(5)
8768(5)
8646(5)
8069(5)
82(5)
97(6)
73(5)
83(5)
67(4)
41(3)
49)3)
64(4)
80(5)
76(5)
58(4)
38(1)
41(1)
43(1)
41(1)
72(2)
105(3)
126(4)
119(4)
82(3)
76(3)
99(3)
98(3)
82(3)
62(2)
63(2)
91(3)
112(3)
103(3)
72(2)
43(3)
52(4)
64(4)
77(5)
72(5)
55(4)
44(3)
56(4)
66(4)
63(4)
58(4)
50(4)
51(4)
51(4)
63(4)
78(5)
68(5)
52(4)
47(3)
76(5)
102(7)
97(7)
84(6)
65(4)
50(3)
68(4)
93(6)
99(7)
98(7)
75(5)
45(3)
66(4)
12 668(7)
11 794(8)
11 761(10)
12 540(12)
13 385(10)
13 449(8)
13 045(6)
12 845(7)
13 106(8)
13 543(8)
13 731(8)
13 476(7)
13 891(7)
14 842(7)
15 705(9)
15 645(9)
14 709(9)
13 844(8)
5669(8)
5417(7)
11 302(1)
10 133(1)
10 836(2)
12 706(2)
8729(4)
12 651(1)
12 707(1)
11 664(1)
13 564(1)
12 588(3)
12 005(4)
11 299(4)
11 185(4)
11 765(3)
13 738(3)
15 008(3)
15 602(3)
14 898(3)
13 641(3)
13 198(3)
12 662(3)
11 547(4)
10 960(3)
11 430(3)
12 205(4)
12 232(5)
11 947(5)
11 589(6)
11 527(5)
11 824(5)
13 638(4)
14 011(5)
14 655(5)
14 964(5)
14 604(5)
13 967(5)
12 339(5)
12 631(4)
12 367(5)
11 817(6)
11 520(6)
11 777(5)
11 107(4)
11 395(6)
10 992(8)
10 298(8)
10 000(6)
10 407(5)
11 877(4)
11 565(5)
11 769(6)
12 292(7)
12 603(7)
12 405(5)
11 023(4)
10 823(5)
10 582(1)
8906(1)
9707(1)
11 835(3)
12 977(3)
13 172(4)
12 222(4)
11 073(3)
10 692(3)
11 450(3)
12 352(3)
12 485(3)
11 671(3)
9369(3)
8882(5)
10 358(7)
11 686(6)
11 553(4)
8471(4)
8746(5)
10 509(6)
11 994(5)
11 781(4)
9193(4)
7479(5)
5982(5)
6240(4)
7984(4)
10 133(6)
9482(7)
9539(8)
10 289(10)
10 945(8)
10 863(7)
10 120(6)
9376(7)
8449(3)
8680(4)
3838(4)
3.2. X-ray diffraction studied
X-ray data for 2 and 3 were collected on a Siemens
P3/PC diffractometer at 296 and 153 K, respectively
(Mo Kh radiation, graphite monochromator, q–2q scan
mode, 25q548 and 25q552°, 14911 and 5109
independent reflections measured, 11073 (F\6|(F))
and 3811 (F\4|(F)) reflections observed for 2 and 3,
respectively). Crystal data at 296
C54H30CuF15GeP2, fw 1161.8, space group P1, a=
13.339(7) A, b=19.575(9) A, c=19.829(12) A, h=
98.22(4)°, i=104.10(4)°, k=94.62(4)°, V=4934(4) A ,
Z=4 (two independent molecules), Dcalc=1.564 g
cm−3, v=1.199 mm−1. Crystal data at 153 K for 3:
C62H46CuF15GeP2, fw 1306.10, space group P212121,
10 718(3)
11 395(4)
11 901(4)
12 506(5)
12 602(5)
12 115(6)
11 517(5)
11 142(4)
11 111(4)
11 505(5)
11 964(5)
12 033(5)
11 618(4)
10 101(4)
9510(5)
9029(5)
9142(7)
9730(6)
10 161(5)
8863(4)
9160(6)
9158(7)
8852(7)
8552(6)
C(6B)
C(7B)
C(8B)
C(9B)
K
for 2:
(
˚
˚
˚
9490(8)
3
˚
C(1OB)
C(11B)
C(12B)
C(13B)
C(14B)
C(15B)
C(16B)
C(17B)
C(18B)
C(19B)
C(20B)
C(21B)
C(22B)
C(23B)
C(24B)
C(25B)
C(26B)
C(27B)
C(28B)
C(29B)
C(30B)
C(31B)
C(32B)
10 378(9)
11 142(8)
10 990(7)
8663(6)
8469(7)
7593(8)
6830(8)
6991(7)
7882(7)
11 744(7)
12 757(8)
13 467(10)
13 152(12)
12 177(12)
11 469(9)
10 652(7)
10 992(8)
10 820(11)
10 349(11)
10 002(10)
10149(8)
9608(6)
˚
˚
˚
a=15.821(2) A, b=18.904(3) A, c=18.926(3) A, V=
5660.3(14) A , Z=4, Dcalc=1.533 g cm−3, v=1.060
3
˚
mm−1. The structures of 2 and 3 were solved by the
direct methods. Besides main molecules the crystal
structure of 3 contains two solvate THF molecules. In
both structures all non-H atoms were refined anisotrop-
ically. The positions of the H atoms were calculated
using a geometrical conditions and do not refined. The
crystal structure of 3 has the polar P212121 space group
symmetry. Therefor it has been also refined with invert
atomic coordinates to obtain the absolute configuration
of molecules 3. Given herein the atomic coordinates
corresponding the absolute configuration of 3 because
of it give the less value of R-factor. The final refine-
ments converged at R=0.081, Rw=0.089, S=3.16 (2)
8558(5)
8040(4)
7457(5)
6827(5)
6767(6)
7315(7)
7966(6)
8966(4)
8778(8)
8448(5)

N.A. Orlo6 et al. / Journal of Organometallic Chemistry 560 (1998) 21–25
25
Table 3 (continued)
Table 3
Atomic coordinates (×103) and equivalent isotropic displacement
coefficients (A ×10 ) for 3
2
3
˚
x
y
z
Ueq
43(3)
62(4)
57(4)
59(4)
47(3)
31(3)
40(3)
53(4)
48(4)
60(4)
55(4)
C(44)
C(45)
C(46)
C(47)
C(48)
C(49)
C(50)
C(51)
C(52)
C(53)
C(54)
O(1)
1937(6)
5545(4)
5683(5)
6358(5)
6883(5)
6752(5)
6694(4)
7002(4)
7661(5)
8023(5)
7739(5)
7083(5)
−877(4)
x
y
z
Ueq
29(1)
1431(7)
1156(7)
1368(7)
1857(6)
2941(5)
2332(5)
2467(7)
3207(7)
3804(7)
3677(6)
5410(11)
9056(10)
6651(12)
5785(14)
6812(14)
6093(12)
9344(22)
8434(19)
8504(33)
8635(22)
−1442(5)
−1594(5)
−1139(6)
−540(5)
811(4)
Cu(1)
Ge(1)
P(1)
P(2)
F(2)
F(3)
F(4)
F(5)
F(6)
3962(1)
5274(1)
4056(1)
5841(1)
5862(1)
4461(2)
3693(3)
2282(3)
1630(3)
2393(2)
4441(3)
4366(3)
3679(4)
3109(3)
3205(2)
3958(2)
3308(3)
2476(3)
2282(3)
2950(3)
3457(4)
3763(4)
3370(5)
2664(5)
2336(4)
2735(4)
3824(4)
4110(5)
4060(5)
3735(5)
3440(5)
3502(4)
3502(4)
3556(4)
3220(4)
2793(4)
2710(4)
3063(4)
5385(4)
5691(5)
5308(7)
4633(7)
4348(6)
4727(5)
5992(4)
6183(4)
6301(6)
6224(6)
6010(6)
5906(5)
6705(4)
6755(5)
7381(8)
7993(6)
7953(5)
7314(5)
5372(4)
5067(5)
4689(5)
4592(5)
4882(5)
5278(5)
6080(4)
28(1)
230(1)
−474(1)
358(1)
4125(1)
5063(1)
2791(1)
3929(3)
4024(4)
4247(4)
4360(3)
4334(3)
4656(3)
6111(4)
7463(4)
7338(3)
5914(3)
2288(3)
964(3)
28(1)
31(1)
30(1)
51(2)
72(2)
72(2)
62(2)
47(2)
53(2)
74(2)
85(3)
69(2)
45(2)
43(2)
55(2)
64(2)
63(2)
50(2)
30(3)
32(3)
51(4)
45(3)
42(3)
32(3)
27(3)
39(3)
54(4)
52(4)
42(4)
32(3)
29(3)
29(3)
36(3)
39(3)
42(3)
32(3)
36(3)
51(3)
77(5)
89(6)
97(6)
58(4)
35(3)
50(3)
66(4)
67(5)
66(4)
50(3)
35(3)
52(3)
86(5)
83(5)
70(5)
52(4)
35(3)
40(3)
53(4)
51(4)
54(4)
44(3)
31(3)
1237(4)
1547(5)
1413(5)
1010(6)
−1366(2)
−2548(3)
−2479(3)
−1220(3)
−15(3)
1703(3)
2416(3)
1847(3)
534(3)
698(5)
F(8)
F(9)
1376(13)
5259(8)
1848(10)
1848(14)
1199(9)
945(8)
5217(22)
4605(15)
4367(20)
5021(24)
2199(11)
137(13)
1686(10)
1575(15)
2061(10)
2329(8)
−599(18)
106(23)
−524(18)
−949(16)
293(13)
238(11)
136(9)
288(18)
145(10)
102(6)
281(22)
255(21)
286(27)
287(23)
O(2)
F(10)
F(11)
F(12)
F(14)
F(15)
F(16)
F(17)
F(18)
C(1)
C(2)
C(3)
C(4)
C(5)
C(1T)
C(2T)
C(3T)
C(4T)
C(5T)
C(6T)
C(7T)
C(8T)
−189(3)
−97(2)
493(3)
1186(3)
2749(3)
4078(3)
4157(5)
4067(6)
4089(7)
4191(6)
4264(5)
4245(5)
5210(5)
5319(5)
6052(7)
6740(6)
6662(6)
5908(5)
3239(5)
2431(5)
1750(5)
1848(6)
2645(6)
3316(5)
5629(5)
5754(6)
6159(7)
6473(8)
6323(9)
5932(6)
5888(5)
6708(5)
7290(6)
7070(7)
6271(8)
5667(6)
4803(5)
4093(6)
3843(7)
4297(7)
4972(7)
5242(6)
2101(5)
2471(6)
1095(7)
1152(6)
787(6)
1648(3)
2182(3)
1624(3)
−631(4)
−1301(4)
−1920(5)
−1884(5)
−1259(5)
−630(4)
746(4)
and R=0.047, Rw=0.047, S=1.42 (3) for observed
reflections. The weight scheme was w=1/[|2(Fo2)+aFo2]
with a equal 0.0003 (2), 0.0003 (3). All calculations were
performed using the SHELXTL-PLUS [6]. The final
atomic coordinates for 2 and 3 were given in Tables 2
and 3, respectively.
C(6)
C(7)
C(8)
C(9)
1395(5)
1777(5)
1469(6)
832(6)
463(4)
744(4)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(37)
C(38)
C(39)
C(40)
C(41)
C(42)
C(43)
488(4)
779(5)
Acknowledgements
1340(5)
1639(5)
1317(4)
−1177(4)
−1851(5)
−2373(6)
−2219(7)
−1594(8)
−1052(5)
181(4)
We are grateful to the X-Ray Structural Centre of
General and Technical Chemistry Division of Russian
Academy of Sciences for kind permission to use a single
crystal diffractometer and the Russian Foundation of
Basic Research (Grants 97-03-32928 and 96-03-32672)
for financial support of this work.
11(5)
545(7)
1234(6)
1417(5)
887(5)
References
[1] (a) B.H. Lipshuts, R.S. Wilhelm, J.A. Kozlovski, Tetrahedron 40
(1984) 5005. (b) G. Koten, J. Organomet. Chem. 400 (1990) 283.
[2] (a) A.H. Cowley, T.M. Elkins, R.A. Jones, C.M. Nunn, Angew.
Chem. Int. Ed. Engl. 27 (1988) 1349. (b) A. Heine, R. Herbst-
Irmer, D. Stalke J. Chem. Soc. Chem. Comm. (1993) 1729. (c) A.
Heine, D. Stalke Angew. Chem. Int. Ed. Engl. 32 (1993) 121.
[3] F. Glocking, K.A. Hooton, J. Chem. Soc. (1962) 2658.
[4] N.A. Orlov, L.N. Bochkarev, A.V. Nikitinsky, S.F. Zhiltsov,
L.N. Zakharov, G.K. Fukin, Ya. Khorshev, J. Organometal.
Chem. 547 (1997) 65.
−862(4)
−1261(5)
−1546(7)
−1398(7)
−975(6)
−689(5)
963(4)
1546(4)
2027(5)
191O(5)
1323(5)
843(5)
[5] G.A. Razuvaev, J. Organometal Chem. 200 (1980) 243.
[6] G.M. Sheldrick. Structure Determination Software Program
Package (PC version). Siemens Analytical X-ray Instruments,
Inc., Madison, WI, 1989.
1247(5)
2126(5)
−394(4)