Two types of intramolecular Lewis-base adducts with the [2-(dimethylamino)ethyl]cyclopentadienyl ligand: Synthesis and crystal structures of {η5:η1-C5H4[(CH 2)2NMe2]}Ni-I and {η5-μ-C5H4[(CH2) 2NMe2]}(Me3P)Ni-InI2

Article abstract of DOI:10.1021/om960712r

The synthesis and reactivity of nickel complexes with the [2-(dimethylamino)ethyl]-cyclopentadienyl ligand (Cp^N) are described. The reaction of NiBr₂ with Cp^NLi leads to the new paramagnetic nickelocene derivative (Cp^N)₂Ni (1), which has been characterized by ¹H and ¹³C NMR, elemental analysis, and mass spectroscopy. Synproportionation of this complex with Ni(CO)₄ affords quantitatively the dimeric nickel complex [Cp^N(CO)Ni]₂ (2). Reductive cleavage of 2 with KC₈ and trapping of the anionic intermediate with Me₃SnCl gives the stannyl-nickel complex Cp^N(CO)Ni-SnMe₃ (4). Reaction of 2 with Ga₂Cl₄ yields the gallium-nickel complex (η⁵-μ-Cp^N)(CO)Ni-GaCl₂ (7) with intramolecular coordination of the dimethylamino group to the gallium center. Oxidative cleavage of 2 with iodine and liberation of CO leads to the intramolecular chelate (η⁵:η¹-Cp^N)Ni-I (3). The compounds (η⁵-μ-Cp^N)(PR₃)Ni-InI₂ with R = C₆H₅ (5) and CH₃ (6) are obtained in good yields by insertion of low-valent indium halides InX (X = Br, I) into the Ni-I bond of 3. X-ray diffraction determinations were carried out for 3 and 6, and for 6, a comparably short Ni-In distance of 241.80(7) pm was found.

Full text of DOI:10.1021/om960712r

5746
Organometallics 1996, 15, 5746-5752
Tw o Typ es of In tr a m olecu la r Lew is-Ba se Ad d u cts w ith
th e [2-(Dim eth yla m in o)eth yl]cyclop en ta d ien yl Liga n d :
Syn th esis a n d Cr ysta l Str u ctu r es of
{η5:η1-C5H4[(CH2)2NMe2]}Ni-I a n d
†,‡
{η5-µ-C5H4[(CH2)2NMe2]}(Me3P )Ni-In I2
Roland A. Fischer,* Sylvain Nlate, Holger Hoffmann, Eberhardt Herdtweck,§ and
J anet Blu¨mel§
Anorganisch-chemisches Institut, Ruprecht-Karls Universita¨t Heidelberg,
Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany
Received August 20, 1996X
The synthesis and reactivity of nickel complexes with the [2-(dimethylamino)ethyl]-
cyclopentadienyl ligand (CpN) are described. The reaction of NiBr2 with CpNLi leads to the
1
new paramagnetic nickelocene derivative (CpN)2Ni (1), which has been characterized by H
and 13C NMR, elemental analysis, and mass spectroscopy. Synproportionation of this complex
with Ni(CO)4 affords quantitatively the dimeric nickel complex [CpN(CO)Ni]2 (2). Reductive
cleavage of 2 with KC8 and trapping of the anionic intermediate with Me3SnCl gives the
stannyl-nickel complex CpN(CO)Ni-SnMe3 (4). Reaction of 2 with Ga2Cl4 yields the
gallium-nickel complex (η5-µ-CpN)(CO)Ni-GaCl2 (7) with intramolecular coordination of the
dimethylamino group to the gallium center. Oxidative cleavage of 2 with iodine and
liberation of CO leads to the intramolecular chelate (η5:η1-CpN)Ni-I (3). The compounds
(η5-µ-CpN)(PR3)Ni-InI2 with R ) C6H5 (5) and CH3 (6) are obtained in good yields by insertion
of low-valent indium halides InX (X ) Br, I) into the Ni-I bond of 3. X-ray diffraction
determinations were carried out for 3 and 6, and for 6, a comparably short Ni-In distance
of 241.80(7) pm was found.
In tr od u ction
deposition (OMCVD) of the respective mixed-metal thin
films. Metallic alloys of selected combinations of group
13 elements with d metals, especially with nickel, e.g.
NiGa4a and NiIn,4b may be of interest as metal contacts
to III/V semiconductor surfaces.4c,d CO ligands may
cause problems in deriving C- and O-free, very pure
metallic alloys from organometallic sources if oxophilic
and/or carbide-forming metals are involved.3 We were
therefore led to investigate some organonickel com-
plexes with the N-donor functionalized [2-(dimethylami-
no)ethyl]cyclopentadienyl ligand (CpN) and their chem-
istry with group 13 halides, aiming at novel intra-
molecular adduct stabilized “CO free” (mixed) metal
compounds, which might be suitable for OMCVD stud-
ies.
The coordination chemistry of functionalized cyclo-
pentadienyl ligands was recently enriched by the intro-
duction of the (dimethylamino)ethyl group at the Cp
ring.1 J utzi et al. have been studying a number of metal
complexes bearing this Lewis base functionalized ligand
and its tetramethyl ring-substituted derivative in de-
tail.2 The benefit of such a ligand, capable of stabilizing
both soft and hard metal centers by intramolecular
adduct formation, was demonstrated. Our interest is
particularly directed toward so-called “all hydrocarbon”3
(i.e. carbonyl group free) and volatile mixed-metal
compounds. Such compounds may be suitable as alter-
native precursors for organometallic chemical vapor
† Organo Group 13 Transition Metal Complexes XVI; XVth Com-
munication see Ref.26
Exp er im en ta l Section
‡ Dedicated to Prof. Dr. Rolf Gleiter on the occasion of his 60th
birthday.
Gen er a l Da ta . All manipulations were undertaken utiliz-
ing standard Schlenk and glovebox techniques under an inert-
gas atmosphere (purified N2 or argon). Solvents were dried
under N2 by standard methods and stored over molecular
sieves (4 Å, Merck; residual water <3 ppm H2O, Karl Fischer).
The NMR spectra of a saturated solution of paramagnetic 1
in C6D6 were recorded on a Bruker MSL 300 NMR spectrom-
eter operating in the low-power mode and equipped with a
conventional 5 mm 1H/13C dual probehead. Measurement
frequencies of 300 (1H) and 75.5 (13C) MHz were applied. A
dead-time delay of 10 µs and a pulse repetition time of 200
§ Anorganisch-chemisches Institut der Technischen Universita¨t
Mu¨nchen, Lichtenbergstrasse 4, D-85747 Garching, Germany.
X Abstract published in Advance ACS Abstracts, November 15, 1996.
(1) (a) Wang, T. F.; Lee, T. Y.; Wen, Y. S.; Liu, L. K. J . Organomet.
Chem. 1991, 403, 353. (b) Wang, T. F.; Lee, J . Y.; Chou, J . W.; Ong, C.
W. J . Organomet. Chem. 1992, 423, 31.
(2) (a) J utzi, P.; Dahlhaus, J .; Kristen, M. O. J . Organomet. Chem.
1993, 450, C1. (b) J utzi, P.; Dahlhaus, J .; Bangel, M. J . Organomet.
Chem. 1993, 460, C13. (c) Dahlhaus, J .; Bangel, M.; J utzi, P. J .
Organomet. Chem. 1994, 474, 55. (d) J utzi, P.; Kristen, M. O.;
Dahlhaus, J .; Neumann, B.; Stammler, H. G. Organometallics 1993,
12, 2980. (e) J utzi, P.; Dahlhaus, J .; Kristen, M. O. J . Organomet.
Chem. 1993, 450, C1. (f) J utzi, P.; Dahlhaus, J .; Coord. Chem. Rev.
1994, 137, 179. (g) J utzi, P.; Kristen, M. O.; Neumann, B.; Stammler,
H. G. Organometallics 1994, 13, 3854. (h) J utzi, P.; Bangel, M. J .
Organomet. Chem. 1994, 480, C18. (i) J utzi, P.; Kleimeier, J . J .
Organomet. Chem. 1995, 486, 287. (j) J utzi, P.; Redeker, T.; Neumann,
B.; Stammler, H. G. J . Organomet. Chem. 1995, 498, 127.
(3) Zinn, A.; Niemer, B.; Kaesz, H. D. Adv. Mater. 1992, 4, 375.
(4) (a) Fraser, B.; Brandt, L.; Stovall, W. K.; Kaesz, H. D.; Khan, S.
I.; Maury, F. J . Organomet. Chem. 1994, 472, 317. (b) Fischer, R. A.;
Kleine, M.; Lehmann, O.; Stuke, M. Chem. Mater. 1995, 7, 1863. (c)
Hampden-Smith, M. J .; Kodas, T. T. Chem. Vap. Dep. 1995, 1, 8. (d)
Fischer, R. A. Chem. Unserer Zeit 1995, 29, 141.
S0276-7333(96)00712-1 CCC: $12.00 © 1996 American Chemical Society

Organo Group 13 Transition Metal Complexes
Organometallics, Vol. 15, No. 26, 1996 5747
ms were integrated within the single pulse sequence. The line
widths ν1/2 at half height of the signals were obtained by the
deconvolution routine of the Bruker Winnmr program. For
the numbering of 1H and 13C nuclei, see Figure 1. J EOL J NM-
GX400 and J NM-GX270 spectrometers and standard data
collection parameters were used for the NMR spectroscopy of
the diamagnetic compounds 2-8 (1H and 13C NMR spectra
were referenced to internal solvent and corrected to TMS). All
J values are reported in Hz. All samples for NMR spectra
were kept in vacuum-sealed NMR tubes. Mass spectra were
recorded with a Finnigan MAT90 instrument (FD spectra); m/z
values are reported for 59Ni and 127I, and normal isotope
distribution was observed. The starting compounds were
prepared as described in the literature. Abbreviations are as
follows: CpN ) η5-C5H4(CH2CH2NMe2), Me ) CH3, Ph ) C6H5.
Elemental analyses were provided by the Microanalytic Labo-
ratory of the Technical University of Munich.
Syn th esis of Bis{[2-(d im eth yla m in o)eth yl]cyclop en ta -
d ien yl}n ick el(II) (1). A cold THF suspension of 2.18 g (10
mmol) of NiBr2 was added to a stirred solution (THF/n-hexane)
of CpNLi (20 mmol) at -78 °C, which was obtained from
reaction of 1.6 M n-BuLi (12.5 mL, 20 mmol) with C5H5[CH2-
CH2N(CH3)2] (CpNH; 2.74 g, 20 mmol). The resulting mixture
was warmed to room temperature and stirred for 2 h. After
evaporation of the solvent, the residue was extracted with
toluene and the crude product was purified by microdistillation
at 120 °C (10-3 Torr, dynamic vacuum, “flask to flask”).
Compound 1 was obtained as a green oil, yield 5.3 g (80%). 1H
NMR (300.0 MHz, C6D6, 25 °C): δ (1H) {ν1/2 [Hz]} -250.1 {820}
(Hb and Hc, C5H4); 5.2 {47} (6H, NCH3); 6.4 {59} (2H, Hâ,
NCH2CH2); 187.8 {305} (2H, HR, NCH2CH2). 13C NMR (75.5
MHz, C6D6, 25 °C): δ (13C) {ν1/2 [kHz]} ) -557.8 {0.39} (CR,
NCH2CH2); 68.8 {0.17} (NCH3); 691.1 {0.46} (Câ, NCH2CH2);
1426 {5.4} (Cb, C5H4); 1567 {5.6} (Cc, C5H4); 1642 {5.6} (Ca,
C5H4). MS (CI): m/z (%) 330 (0.7) [M+], 136 (1.4) [CpN +], 58
(100) [CH2N(CH3)2+]. Anal. Calcd for C18H28N2Ni: C, 65.42;
H, 8.55; N, 8.48; Ni, 17.55. Found: C, 65.73; H, 8.66; N, 8.60;
Ni, 17.43.
toluene. The crude product was purified by crystallization at
-30 °C. Complex 3 was obtained as analytically pure brown-
violet crystals in 85% yield (2.2 g). 1H NMR (399.78 MHz,
CD2Cl2, 25 °C): δ 0.42 (m, br, 2H, NCH2CH2); 2.51 (s, 6H,
NCH3); 3.39 (m, br, 2H, NCH2CH2); 5.26-5.31 (2 × br, 2 ×
2H, C5H4). 13C{1H} NMR (100.5 MHz, CD2Cl2, 25 °C): δ 10.07
(NCH2CH2); 20.3 (NCH3); 70.3 (NCH2CH2); 124.1 (Cipso of
C5H4); 127.0-127.8 (C5H4). MS (CI): m/z (%) 321 (51) [M+],
194 (48) [M+ - I], 136 (4) [CpN +]. Anal. Calcd for C9H14
-
INNi: C, 33.60; H, 4.38; N, 4.35; I, 39.45; Ni, 18.22. Found:
C, 34.00; H, 4.45; N, 4.33; I, 38.85; Ni, 18.92.
Syn th esis of {η5-[2-(Dim eth yla m in o)eth yl]cyclop en ta -
d ien yl}(tr im eth ylsta n n yl)n ick el(II) (4). A THF solution
(20 mL) of 2 (0.891 g, 2 mmol) was added to a stirred THF
suspension of C8K (0.540 g, 4 mmol) at -78 °C. The resulting
mixture was warmed to room temperature and stirred for 10
min. After the resulting orange solution was cooled to -78
°C, a solution of Me3SnCl (0.797 g, 4 mmol) in 15 mL of THF
was added. The stirred mixture was warmed to room tem-
perature over the course of 1 h. After evaporation of the
solvent, the residue was extracted with n-pentane. Product 4
was obtained as a yellow-orange oil, yield 1.392 g (90%). 1H
NMR (399.78 MHz, C6D6, 25 °C): δ 0.46 (s, 9H, SnCH3); 2.08
(s, 6H, NCH3); 2.36-2.38 (2 × m, br, 2 × 2H, NCH2CH2); 4.72-
5.10 (2 × m, br; 2 × 2H, C5H4). 13C{1H} NMR (100.5 MHz,
C6D6, 25 °C): δ -2.4 (SnCH3); 28.9 (NCH2CH2); 45.5 (NCH3);
61.1 (NCH2CH2); 85.9-102.1 (C5H4); 115.2 (Cipso of C5H4).
119Sn{1H} NMR (C6D6, 25 °C): δ 107.7. IR (n-pentane): 1996
cm-1 (ν(CO)). MS (CI): m/z (%) 387 (67.8) [M+], 388 (24) [CpN
-
2
Ni2+], 359 (100) [M+ - CO], 222 (6.33) [M+ - SnMe3], 136 (4)
[CpN +]. Anal. Calcd for C13H23NNiOSn: C, 40.37; H, 5.99;
N, 3.62; Ni, 15.18. Found: C, 41.13; H, 5.42; N, 3.77; Ni, 14.85.
Syn th esis of {η5-µ-[2-(Dim eth ylam in o)eth yl]cyclopen ta-
d ien yl}(tr ip h en ylp h osp h in o)(d iiod oin d io)n ick el(II) (5)
a n d {η5-µ-[2-(Dim eth yla m in o)eth yl]cyclop en ta d ien yl}-
(tr im eth ylph osph in o)(diiodoin dio)n ickel(II) (6). A sample
of 3 (0.322 g, 1 mmol), freshly sublimed InBr (0.195 g, 1 mmol),
and triphenylphosphine (0.262 g, 1 mmol) were suspended in
20 mL of THF at -78 °C. The brown-violet suspension turned
immediately red to give the intermediate {η5-[2-(dimethyl-
amino)ethyl]cyclopentadienyl}(triphenylphosphino)iodonickel-
(II) (see Scheme 1). The resulting mixture was warmed to
room temperature and stirred for another 3 h. A sample of
NaI (0.300 g, 2 mmol) was added to the resulting yellow-green
solution. The reaction mixture was stirred for another 2 h,
and the solvent was removed in vacuo. The residue was
washed with 15 mL of n-pentane and extracted with toluene.
The crude product was purified by crystallization in toluene
at -30 °C. Compound 5 was obtained as yellow-green crystals
in 85% yield (0.70 g). The preparation of 6 was analogous to
that for 5. Complex 6 was obtained with 90% yield as dark
green crystals.
Syn th esis of Bis[ca r bon yl{[2-(d im eth yla m in o)eth yl]-
cyclop en ta d ien yl}n ick el(I)] (2). Meth od a . A toluene
solution of 1.32 g (4 mmol) of 1 and Ni(CO)4 (1.1 mL, 8 mmol)
was heated at 80 °C for 1 h. After evaporation of the solvent,
the residue was extracted with n-pentane. The nickel carbonyl
dimer 2 was obtained quantitatively as a deep red oil, yield
1.75 g (98%).
Meth od b. At -35 °C Ni(CO)4 (3.5 mL in 15 mL of THF)
was added to a solution of CpNLi, which was obtained from
reaction of 1.6 M n-BuLi (12 mL, 14.6 mmol) with C5H4[CH2-
CH2N(CH3)2] (CpNH; 2.00 g, 14.6 mmol at -78 °C) in 100 mL
of THF. The resulting mixture was warmed to room temper-
ature and was heated to reflux for 14 h. At room temperature
CuCl (1.45 g, 14.6 mmol) was added, and the mixture was
heated to reflux again for 2 h. After evaporation of the solvent,
the residue was extracted with n-pentane. The nickel carbonyl
Characterization data for 5 are as follows. 1H NMR (399.78
MHz, CD2Cl2, 25 °C): δ 2.57 (s, 6H, NCH3), 2.62 (AA′BB′, 2H,
NCH2CH2); 2.93 (AA′BB′, 2H, NCH2CH2); 4.83 (br, 2H, C5H4);
5.30 (br, 2H, C5H4); 7.36-7.61 (m, 15H, PPh3). 13C{1H} NMR
(100.5 MHz, CD2Cl2, 25 °C): δ 24.2 (NCH2CH2); 46.8 (NCH3);
57.0 (NCH2CH2); 90.6 (C5H4); 92.4 (Cipso of C5H4); 93.0 (C5H4);
128.3-136.0 (Ph). 31P{1H} NMR (169.9 MHz, CD2Cl2, 25 °C,
H3PO4 ext.): δ 48.7 (PPh3). MS (CI): m/z (%) 825 (not
detected) [M+], 583 (2.8) [M+ - InI], 456 (12) [M+ - InI2], 369
(4.8) [InI2+], 321 (12.3) [M+ - {In(I)(PPh3)}], 263 (100) [Ph3-
PH+], 262 (30.4) [Ph3P+], 136 (2) [CpN +]. Anal. Calcd for
1
dimer 2 was obtained as a deep red oil, yield 3.25 g (50%). H
NMR (399.78 MHz, C6D6, 25 °C): δ 2.10 (s, 12H, NCH3); 2.39-
2.41 (2 × m, br, 4 × 4H, NCH2CH2); 5.11 (br, 4H, C5H4); 5.19
(br, 4H, C5H5). 13C{1H} NMR (100.5 MHz, C6D6, 25 °C): δ
25.2 (NCH2CH2); 46.3 (NCH3); 59.8 (NCH2CH2); 93.3-94.1
(C5H4); 109.2 (Cipso of C5H4); 228.3 (CO). IR (n-pentane): 1888,
1846 cm-1 (ν(CO)). MS (CI): m/z (%) 445 (not detected) [M+],
389 (5) [M+ - 2(CO)], 388 (24) [CpN2Ni2+], 330 (100) [M+
-
Ni(CO)2], 222 (42) [CpN(CO)Ni+], 194 (2) [CpNNi+], 136 (1)
[CpN +]. Anal. Calcd for C20H28N2Ni2O2: C, 53.88; H, 6.33;
N, 6.28; Ni, 26.33. Found: C, 54.36; H, 6.52; N, 6.42; Ni, 25.51.
Syn t h esis of {η5:η1-[2-(Dim et h yla m in o)et h yl]cyclo-
p en ta d ien yl}iod on ick el(II) (3). A THF solution (20 mL) of
1.02 g (4 mmol) of I2 was added at -78 °C over a period of 30
min to a stirred THF solution of 2 (1.8 g, 4 mmol). The
resulting mixture was warmed to room temperature and
stirred for 2 h. After evaporation of the solvent, the residue
was washed with 15 mL of n-pentane and extracted with
C
27H29I2InNNiP: C, 39.24; H, 3.54; N, 1.69; I, 30.74; Ni, 7.11;
In, 13.90. Found: C, 38.76; H, 3.55; N, 1.56; I, 30.27; Ni, 6.97;
In, 13.10.
Characterization data for 6 are as follows. 1H NMR (399.78
2
MHz, C6D6, 25 °C): δ 1.01 (d, J H-P ) 9.3 Hz, 9H, P(CH3)3);
1.85 (AA′BB′, 2H, NCH2CH2); 2.07 (AA′BB′, 2H, NCH2CH2);
2.18 (s, 6H, NCH3); 4.90 (m, 2H, C5H4); 5.00 (m, 2H, C5H4).
1
13C{1H} NMR (100.5 MHz, C6D6, 25 °C): δ 21.0 (d, J C-P
)
31.2 Hz, P(CH3)3); 24.2 (CH2CH2N); 45.9 (NCH3); 55.9

5748 Organometallics, Vol. 15, No. 26, 1996
Fischer et al.
Ta ble 1. Cr ysta llogr a p h ic Da ta for Com p ou n d s 3
a n d 6
Ta ble 2. Selected Bon d Dista n ces (p m ) a n d An gles
(d eg) for Com p ou n d 3a
3
6
I-Ni
250.02(9)
196.0(5)
173.2
212.8(6)
213.0(5)
214.2(7)
211.9(7)
199.7(7)
151.7(10)
N-C(8)
146.6(8)
147.0(8)
136.8(10)
141.1(10)
143.3(9)
137.2(11)
144.1(10)
149.2(11)
137.9(14)
Ni-N
N-C(9)
formula
fw
cryst color, habit
C9H14INNi
321.8
brown-violet,
prism
orthorhombic
Pbca (No. 61)
C12H23I2InNNiP
705.9
dark green,
column
orthorhombic
P212121 (No. 19)
Ni-Cp
Ni-C(1)
Ni-C(2)
Ni-C(3)
Ni-C(4)
Ni-C(5)
N-C(7)
C(1)-C(2)
C(1)-C(5)
C(2)-C(3)
C(3)-C(4)
C(4)-C(5)
C(5)-C(6)
C(6)-C(7)
cryst syst
space group
cryst dimens, mm
temp, K
a, pm
0.23 × 0.15 × 0.15 0.32 × 0.32 × 0.24
303 ( 1
900.0(1)
1320.6(1)
1891.3(1)
2247.9(3)
8
233 ( 1
928.2(1)
978.9(1)
2119.5(2)
1925.8(3)
4
I-Ni-N
I-Ni-Cp
N-Ni-Cp
Ni-N-C(7)
Ni-N-C(8)
Ni-N-C(9)
103.3(2)
134.0
122.7
107.4(4)
113.3(4)
111.6(4)
C(7)-N-C(8)
C(7)-N-C(9)
C(8)-N-C(9)
C(5)-C(6)-C(7)
N-C(7)-C(6)
104.1(6)
111.2(7)
109.1(5)
112.1(8)
116.2(8)
b, pm
c, pm
V, 106 pm3
Z
d
calcd, g cm-3
1.902
44.2
2.206
54.5
µ(Mo KR), cm-1
a
Cp denotes the centre of gravity in the C5H4R part of the CpN
scan type, mode
image plate,
oscillation
120 per image
25.1; (h,(k,(l
Lp
image plate,
rotation
120 per image
24.9; (h,(k,(l
Lp; abs
ligand.
scan time, s
θ
max, deg; octants
corrections
with a rotating anode (ENRAF-Nonius FR591; 50 kV; 60 mA;
3.0 kW) and graphite-monochromated Mo KR radiation. The
data collection was performed at 303 ( 1 K within the θ range
of 1.6° < θ < 25.1° with an exposure time of 2 min per image
(oscillating scan modus for æ ) 0.0-150.0° and æ ) 160-360°
with ∆æ ) 1°). A total number of 27 224 reflections were
collected, from which a sum of 1864 independent reflections
remained and were used for all calculations. Data were
corrected for Lorentz and polarization effects. Corrections for
intensity decay, absorption µ ) 44.2 cm-1, and extinction were
not necessary and were not applied. The unit cell parameters
were obtained by least-squares refinements of 1571 reflections
with the program Cell.5,6 The structure was solved with direct
methods and difference Fourier syntheses.7,8 All 12 “heavy
atoms” of the asymmetric unit were anisotropically refined.
All H positions were calculated in ideal geometry riding on
the parent carbon atom. The isotropic displacement param-
eters were kept constant (Uiso ) 1.3Ueq(C)). Full-matrix least-
no. of rflns collctd
R(merge)
no. of unique data
no. of rflns included
(NV)
27224
24201
2
2
0.032 (Fo
1864
)
0.032 (Fo
3096
)
1864
3096
no. of variables (NO)
data:variable ratio
R1a
109
17.1
0.0565
0.1117
0.953
-0.02(2)
<0.005
255
12.1
0.0188
0.0449
1.164
wR2a
GOFa
Flack param
largest shift/error
<0.001
max/min resid electron +2.38/-0.81
+0.43/-0.52
dens, e Å-3
weighting scheme
SHELXL
(0.0715; 0.00)
SHELXL
(0.0147; 3.18)
R1 ) ∑||Fo| - Fc|/∑|Fo|, wR2 ) [∑w(Fo - Fc2)2/∑w(Fo2)2]1/2
,
a
2
and GOF ) [∑w(Fo - Fc2)2/(NO - NV)]1/2
.
2
2
squares refinements were carried out by minimizing ∑w(Fo
- Fc2)2 and stopped at shift/error <0.005: wR2 ) 0.1117, and
R1 ) 0.0565. In the final difference map, the largest peaks,
+2.38 and -0.81 e/Å3, are located around the iodine atom.
Neutral atom scattering factors for all atoms and anomalous
dispersion corrections for the non-hydrogen atoms were taken
from ref 9. All calculations were performed on a DEC 3000
AXP workstation with the STRUX-V system,8 including the
programs PLATON-92,10 PLUTON-92,10 SIR-92,7 and SHELX-
93.11 Selected bond lengths and angles are given in Table 2.
Further details of the crystal structure investigation are
available on request from the Fachinformationszentrum
Karlsruhe, Gesellschaft fu¨r wissenschaftlich-technische Infor-
mation mbH, D-76344 Eggenstein-Leopoldshafen 2, Germany,
on quoting the depository number CSD-405435, the names of
the authors, and the journal citation, or from the author E.H.
X-r a y Sin gle Cr ysta l Str u ctu r e Deter m in a tion of {η5-
µ-[2-(d im eth yla m in o)eth yl]cyclop en ta d ien yl}(tr im eth yl-
p h osp h in o)(d iiod oin d io)n ick el(II) (6). Suitable crystals
(CH2CH2N); 89.4-89.6 (C5H4), 91.2 (Cipso of C5H4). 31P{1H}
NMR (169.9 MHz, C6D6, 25 °C, H3PO4 ext.): δ -12.4 (PMe3).
MS (CI): m/z (%) 639 (not detected) [M+], 321 (3.3) [M+ - {In-
(I)PMe3}], 136 (100) [CpN +]. Anal. Calcd for C12H23I2-
InNNiP: C, 22.53; H, 3.62; N, 2.18; I, 39.68; Ni, 9.17; In, 17.95.
Found: C, 21.53; H, 3.42; N, 1.98; I, 38.24; Ni, 8.88; In, 17.4.
Syn th esis of Ca r bon yl{η5-µ-[2-(d im eth yla m in o)eth yl]-
cyclop en ta d ien yl}(d ich lor oga llio)n ick el(II) (7). A THF
solution (20 mL) of 2 (0.892 g, 2 mmol) was added at -78 °C
to a stirred THF solution of 0.844 g (3 mmol) of Ga2Cl4. The
resulting mixture was warmed to room temperature, and
stirred for 3 days. After evaporation of the solvent, the residue
was extracted with toluene. The crude product could be
purified by crystallization at -30 °C. Compound 7 was
obtained as orange crystals in 50% yield (0.727 g). 1H NMR
(399.78 MHz, C6D6, 25 °C): δ 1.61 (AA′BB′, 2H, NCH2CH2);
1.95 (AA′BB′, 2H, NCH2CH2); 1.98 (s, 6H, NCH3), 4.79 (t, 3J H-H
3
) 2.2 Hz, 2H, C5H4); 5.20 (t, J H-H ) 2.2 Hz, 2H, C5H4). 13C-
{1H} NMR (100.5 MHz, C6D6, 25 °C): δ 22.8 (CH2CH2N); 44.1
(NCH3); 55.5 (CH2CH2N); 89.6-92.0 (C5H4), 93.3 (Cipso of C5H4).
IR (toluene): 2012.8 cm-1 (ν(CO)). MS (CI): m/z (%) 363 (1)
[M+], 141 (100) [GaCl2+]. Anal. Calcd for C10H14Cl2GaNNiO:
C, 33.03; H, 3.88; N, 3.85; Ga, 19.17; Cl, 19.50; Ni, 16.14.
Found: C, 33.26; H, 3.84; N, 3.60; Ga, 19.3; Cl, 19.39; Ni, 15.19.
(5) IPDS Operating System, Version 2.6; Stoe&Cie GmbH, Darm-
stadt, Germany, 1995.
(6) Schu¨tt, W.; Herdtweck, E.; Hahn, F.; Kreissl, F. R. J . Organomet.
Chem. 1993, 443, C33 and references cited therein.
(7) Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A.;
Burla, M. C.; Polidori, G.; Camalli, M. SIR-92; University Bari, Bari,
Italy, 1992.
(8) Artus, G.; Scherer, W.; Priermeier, T.; Herdtweck, E. STRUX-
V, a Program System To Handle X-ray Data; TU Mu¨nchen, Mu¨nchen,
Germany, 1994.
(9) International Tables for Crystallography; Wilson, A. J . C., Ed.;
Kluwer Academic: Dordrecht, The Netherlands, 1992; Vol. C, pp 500-
502 (Table 6.1.1.4), 219-222 (Table 4.2.6.8), 193-199 (Table 4.2.4.2).
(10) Spek, A. L. PLATON-92-PLUTON-92, an Integrated Tool for
the Analysis of the Results of a Single Crystal Structure Determina-
tion. Acta Crystallogr. 1990, A46, C34.
X-r a y Sin gle Cr ysta l Str u ctu r e Deter m in a tion of {η5:
η1-[2-(Dim eth ylam in o)eth yl]cyclopen tadien yl}iodon ickel-
(II) (3). Suitable crystals were grown by slow solvent diffusion
techniques from toluene/n-pentane mixtures at -30 °C. Crys-
tal data together with details of the data collection and
structure refinement are listed in Table 1. Preliminary
examination and data collection were carried out on an
imaging plate diffraction system (IPDS; Stoe&Cie) equipped
(11) Sheldrick, G. M. J . Appl. Crystallogr., in press; Program
SHELXL-93; University of Go¨ttingen, Go¨ttingen, Germany, 1993.

Organo Group 13 Transition Metal Complexes
Organometallics, Vol. 15, No. 26, 1996 5749
Ta ble 3. Selected Bon d Dista n ces (p m ) a n d An gles
(d eg) for Com p ou n d 6a
Sch em e 1
(1)-In
279.82(5)
278.73(6)
241.80(7)
233.2(4)
211.6(1)
172.8
210.1(4)
211.6(6)
210.6(7)
207.9(6)
212.8(5)
181.2(7)
P-C(2)
182.0(8)
179.6(7)
148.2(7)
147.9(8)
147.3(8)
150.7(9)
150.0(8)
143.5(8)
143.4(7)
138.7(9)
140.7(9)
141.1(8)
I(2)-In
In-Ni
P-C(3)
N-C(5)
In-N
N-C(6)
Ni-P
N-C(7)
Ni-Cp
C(4)-C(5)
C(4)-C(11)
C(11)-C(12)
C(11)-C(15)
C(12)-C(13)
C(13)-C(14)
C(14)-C(15)
Ni-C(11)
Ni-C(12)
Ni-C(13)
Ni-C(14)
Ni-C(15)
P-C(1)
I(1)-In-I(2)
I(1)-In-Ni
I(1)-In-N
I(2)-In-Ni
I(2)-In-N
Ni-In-N
98.83(2)
121.64(2)
99.1(1)
125.93(2)
96.66(9)
109.1(1)
94.39(4)
126.5
C(1)-P-C(2)
C(1)-P-C(3)
C(2)-P-C(3)
In-N-C(5)
102.0(3)
103.1(3)
102.6(4)
108.1(3)
111.5(3)
110.3(3)
108.2(5)
110.7(4)
108.0(5)
119.5(5)
116.1(5)
In-N-C(6)
In-N-C(7)
In-Ni-P
C(5)-N-C(6)
C(5)-N-C(7)
C(6)-N-C(7)
C(5)-C(4)-C(11)
N-C(5)-C(4)
In-Ni-Cp
P-Ni-Cp
Ni-P-C(1)
Ni-P-C(2)
Ni-P-C(3)
139.1
119.1(2)
113.3(3)
114.5(2)
a
See footnote a in Table 2.
were grown by slow solvent diffusion techniques from toluene
at -30 °C. Crystal data together with details of the data
collection and structure refinement are listed in Table 1.
Preliminary examination and data collection were carried out
on an imaging plate diffraction system (IPDS; Stoe&Cie)
equipped with a rotating anode (ENRAF-Nonius FR591; 50
kV; 80 mA; 4.0 kW) and graphite-monochromated Mo KR
radiation. The data collection was performed at 233 ( 1 K
within the θ range of 1.9° < θ < 24.9° with an exposure time
of 2 min per image (rotating scan modus for æ ) 0.0-360°
with ∆æ ) 1°). A total number of 24 201 reflections were
collected, from which a sum of 3096 independent reflections
remained and were used for all calculations. Data were
corrected for Lorentz, polarization, and absorption effects (µ
) 44.2 cm-1; program Decay5,6). Corrections for intensity
decay and extinction were not necessary and were not applied.
The unit cell parameters were obtained by least-squares
refinements of 1805 reflections with the program Cell.5,6 The
structure was solved with direct methods and difference
Fourier syntheses.7,8 All 18 “heavy atoms” of the asymmetric
unit were anisotropically refined. All hydrogen positions were
found and refined free with individual isotropic displacement
parameters. Full-matrix least-squares refinements were car-
dimer 2 as a deep red oil. The trinuclear cluster
compound CpN3Ni3(µ3-CO)2 was not detected in the
reaction mixture. This is interesting, because in the
case of the parent Cp ligand the corresponding nickel
cluster is usually formed as a byproduct in 30-40%
yield.12 Alternatively, a one-pot synthesis of 2 is pos-
sible (Scheme 1), but the yields are not better. Oxida-
tive cleavage of the Ni-Ni bond of 2 with iodine in THF
solution gives the CO-free intramolecular Lewis base
adduct 3. The direct synthesis of 3 from NiI2 and CpN-
Li was attempted but could not be carried out success-
fully.
Reductive cleavage of the Ni-Ni bond of 2 with
potassium graphite (KC8) in THF yields the anion
[CpNNi(CO)]- as a highly reactive species (identified by
its infrared ν(CO) absorption) which can be trapped
quantitatively by the addition of various electrophiles
(Scheme 1). Addition of Me3SnCl, for example, leads
to the Ni-Sn compound 4. It was not possible to
liberate the CO substituent of 4 by heating (110 °C) and
to coordinate the amine donor to the Ni center. Irradia-
tion with UV light (250 nm, Hg lamp) quickly gave
unspecific decomposition. The reactivity of compound
3 with low-valent group 13 halides illustrates its
synthetic potential as a starting material to achieve the
2
2 2
ried out by minimizing ∑w(Fo - Fc
) and stopped at shift/
error <0.001: wR2 ) 0.0449, and R1 ) 0.0188. In the final
difference map, the largest peaks, +0.43 and -0.52 e/Å3, are
located around the metal atoms. The correct polarity of the
crystal is proved by refining Flack’s parameter to -0.02(2).
Neutral atom scattering factors for all atoms and anomalous
dispersion corrections for the non-hydrogen atoms were taken
from ref 9. All calculations were performed on a DEC 3000
AXP workstation with the STRUX-V system,8 including the
programs PLATON-92,10 PLUTON-92,10 SIR-92,7 and SHELX-
93.11 Selected bond lengths and angles are given in Table 3.
Syn th esis a n d Rea ctivity
According to Scheme 1, the key compound CpN2Ni (1)
is readily available as a green distillable (120 °C, 10-2
Torr, dynamic vacuum) oil in very good yield (80%) by
the reaction of a suspension of dry NiBr2 in THF with
n
CpNLi prepared in situ (from CpNH and BuLi). Com-
plex 1 reacts rapidly with excess Ni(CO)4 in toluene at
80 °C to give quantitatively (98%) the nickel carbonyl
(12) Fischer, E. O.; Palm, C. Chem. Ber. 1958, 91, 1725.

5750 Organometallics, Vol. 15, No. 26, 1996
Fischer et al.
desired nickel compounds, free of CO ligands. The new
insertion products 5 and 6 are prepared by treatment
of 3 with InIBr. In order to achieve this insertion of
InIX (X ) Cl, Br, I) into the Ni-I bond of 3, however,
the presence of PPh3 or PMe3 is necessary (Scheme 1).
Without this ancillary ligand 3 does not react cleanly
with InIX. Interestingly, the related chemistry of
Cp(PPh3)Ni-Br with InIBr is also very much dependent
on the solvent and the presence of Lewis base ligands.13
Treatment of 3 with InIBr and phosphine ligands
immediately gives red solutions, which turn slowly
yellow-green as the final color. Apparently, the primary
step of this reaction involves the substitution of the
amine ligand by the softer phosphine to give intermedi-
ates, which then react smoothly with InBr to yield the
Ni-In compounds 5 and 6 with the amine ligand now
intramolecularly coordinated to the “harder” indium
center. The presence of NaI is only necessary to obtain
the symmetrically substituted InI2 complex by salt
metathesis.
trum of the two methylene groups for 2 shows some
unusual temperature dependence. Because of the ac-
cidentally very small chemical shift difference of the
methylene protons, no simple spin system results at
room temperature. A poorly resolved quintet is ob-
served instead of the expected set of two AB2 spin
systems. Cooling did not improve the resolution. Upon
stepwise heating to 348 K, however, a very sharp singlet
developed gradually with the relative intensity of 4
hydrogen equivalents relative to the N-CH3 groups.
This effect results from the small temperature depen-
dency of the chemical shift of the hydrogen atoms under
consideration, leading to the magnetic equivalence of
all the methylene protons. Consequently, the expected
AB2 spin systems collapse to one singlet. An attempt
to obtain a simple derivative of 2 to check the NMR
spectroscopic properties of 2 somewhat further failed,
however: the treatment of 2 with HBF4 surprisingly led
to complete decomposition. This finding contrasts with
the behavior of [Cp*N(CO)Ni]2, from which compound
the respective protonated derivative is reported.16
The 1H NMR spectra of 5 and 8 clearly show the
features indicative of an intramolecular adduct1,2 in-
volving the indium center in these cases. Compound 8
shows the ν(CO) IR absorption at 2002 cm-1, which
compares to the value of 1997 cm-1 for the related
compound Cp(CO)Ni-InBr2(NC7H13), whose structure
was determined.13a The 31P NMR shift of 5 is very
similar to the respective value for the related compound
Cp(PPh3)Ni-InBr2(OdPPh3), whose structure is also
known,13b and indicates the presence of a Ni-PPh3 unit
rather than an indium-phosphorus linkage. The pref-
erence of In-N over Ni-P follows the HSAB (hard and
soft acids and bases) concept.
The mixed-metal nickel gallium complex 7 (Scheme
1) was prepared by insertion of Ga2Cl4 into the Ni-Ni
bond of 2, but a suitable crystal for X-ray analysis could
not be obtained. A homologous mixed-metal nickel
indium complex had been derived from 2 by a similar
route.13a Compound 7 sublimed unchanged under mod-
erate conditions (10-3 Torr, 120 °C). Therefore, it can
be used as a precursor for OMCVD of nickel gallium
alloy thin films. The synthesis of related “CO-free”
nickel gallium complexes similar to the Ni-In com-
“
pounds 5 and 6 requires GaII”, which is not known as
a pure compound but can be prepared in situ according
to Green et al.14 Work in this direction is currently in
progress. The synthetic potential of complex 3 is
especially illustrated by the quantitative synthesis of
the first structurally characterized intramolecularly
adduct stabilized silyl-silylene {η5-µ-C5H4[(CH2)2N-
Me2]}[(SiMe3)2MeSi]NidSiMe2, which we reported re-
cently.15
Compound 4 exhibits a Ni-CO unit (1996 cm-1
)
similar to 8 and some downfield shift of the R-CH2 group
but a less resolved AA′BB′ spin system at room tem-
perature. A tetracoordinate trialkyltin center is much
less Lewis acidic than a tricoordinate dihalogenoindium
group. Therefore, it is unlikely that the aminoethyl
group is coordinated to the tin atom at room tempera-
ture. The 119Sn NMR data for 4 (δ 107.6) is almost
identical with the value of 109.7 of the closely related
cyclopentadienyl complex [Cp(CO)Ni-SnMe3].17 It fol-
lows that the amino atom of 4 is not coordinated to the
tin atom. This situation may change if more Lewis
acidic tin centers are employed (e.g. SnOR3).
Sp ectr oscop ic Ch a r a cter iza tion
The presence of a stable intramolecular Lewis base
adduct, involving the (dimethylamino)ethyl unit, is
1
indicated in the H NMR spectra by a downfield shift
of the methylene protons in a position R to the terminal
N atom of the side chain.1,2 Furthermore, the multiplic-
ity of the spin system of the CH2CH2 moiety changes
from a simple AB2 system of the free side chain to a
more or less resolved AA′BB′ system upon coordination
to the Lewis acid center, because of the restricted
Compound 3 represents a new member of the series
of intramolecularly complexed CpN ligands at 3d metals.
1
The H NMR data for 3 are similar to those for other
related systems such as Cp*NCoI2.2e The formation of
7 is proved by NMR and mass spectroscopy. The 1H
NMR spectra clearly show the features indicative of an
intramolecular adduct1,2 involving the gallium center
in these cases. The methylene groups exhibit two
partially resolved AA′BB′ spin systems similar to those
for complex 5, 6, and the known complex 8.13a The
electron impact mass spectrum of 7 shows the molecular
peak.
1
conformational freedom.1,2 The H and 13C NMR data
for the noncoordinated ethylamino moiety of 2 are very
similar to the values reported for the permethylated
derivative [Cp*N(CO)Ni]2 (Cp*N ) 1-[2-dimethylamino)-
ethyl]-2,3,4,5-tetramethylcyclopentadienyl), the struc-
ture of which is known, proving the existence of the free
1
uncomplexed aminoethyl group.16 The H NMR spec-
(13) (a) Weiss, J .; Frank, A.; Herdtweck, E.; Nlate, S.; Mattner, M.
R.; Fischer, R. A. Chem. Ber. 1996, 129, 297. (b) Weiss, J .; Priermeier,
T.; Fischer, R. A. Inorg. Chem. 1996, 35, 71.
(14) Green, M. L. H.; Mountford, P.; Smout, G. J .; Speel, S. R.
Polyhedron 1990, 9, 2763.
(15) Nlate, S.; Herdtweck, E.; Fischer, R. A. Angew. Chem., Int. Ed.
Engl. 1996, 35, 1861.
(16) J utzi, P.; Redeker, T.; Neumann, B.; Stammler, H. G. J .
Organomet. Chem. 1995, 498, 127.
(17) Fischer, R. A.; Behm, J .; Herdtweck, E.; Kronseder, C. J .
Organomet. Chem. 1992, 437, C29 and references cited therein.
Spectroscopic data for an authentic sample of Cp(CO)Ni-SnMe3 for
comparison with the new complex 4 are as follows. (red-orange oil).
1H NMR (399.78 MHz, C6D6, 25 °C): δ 2.42 (s, 9H, SnCH3); 7.00 (C5H5).
13C{1H} NMR (100.5 MHz, C6D6, 25 °C): δ -2.7 (SnCH3); 89.9, 93.9,
112.9 (C5H5); 192.1 (CO). 119Sn{1H} NMR (C6D6, 25 °C): δ 109.7. IR
(n-pentane): 2000 cm-1
.

Organo Group 13 Transition Metal Complexes
Organometallics, Vol. 15, No. 26, 1996 5751
F igu r e 1. Paramagnetic 13C NMR spectrum of complex
1.
F igu r e 2. Molecular structure of 3 in the solid state
(PLATON drawing; the thermal ellipsoids are represented
at a 50% probability level). Hydrogen atoms are omitted
for clarity.
1
Although compound 1 is paramagnetic, its H and 13C
NMR spectra can be recorded easily. The 13C NMR
spectrum of 1 is displayed in Figure 1. Due to the
excellent solubility of 1, no special equipment is needed
as described elsewhere.18 As expected, the line width
of the signals decreases with increasing distance of the
corresponding nuclei from the paramagnetic center. The
1H and 13C NMR signal assignments can be made in
analogy to the known ones of [MeCp]2Ni,19 [EtMe4-
Cp]2Ni,20 and [EtCp]2Ni.21 The chemical shifts of 1 are
in good agreement with those reference compounds.
(Note, however, that the sign convention has been
changed since the earlier publications.20,21) The 13C
NMR signals of the ring carbon atoms are well resolved
(Figure 1, expanded region), while the ring 1H NMR
signals are overlapping. The latter could possibly by
about 100°.13b The angle N-C(7)-C(6) of 116.2(8)°
indicates some distortion of the tetrahedral surround-
ings of C(7) caused by the Ni-N bond formation. The
corresponding N-C-C angles of the related compounds
CpNMo(CO)2I1b and CpNML2 (M ) Mn, L ) CO;1a M )
Co, Rh, Ir2e,h) are somewhat smaller (110-112°). Those
complexes exhibit pentacoordinate (Mo) and tetracoor-
dinate (Mn, Co, Rh, Ir) d metal centers. The aminoethyl
unit is apparently conformatively flexible enough to
coordinate to various d metal centers of different steric
demand and coordination number. In summary, how-
ever, a significant stress on the system of 3 is reflected
by the structural parameters, i.e. asymmetric coordina-
tion of the Cp ring, the “large” angle N-C(6)-C(7), and
the comparably large deviation of C(6) from the best Cp-
ring plane of 37 pm toward the Ni atom. Complex 3 is
chiral in the solid state, which is caused by the confor-
mative requirements of the intramolecular adduct ring
(zigzag fashion). Due to the disorder of C(6) and C(7),
however, the two enantiomers cannot be distinguished.
In solution the molecule appears to have Cs symmetry,
which is caused by a very fast motion of the side chain,
so that only an averaged spectrum is observed.
1
resolved by switching from H to 2H NMR spectroscopy
(natural abundance!), which provides narrower lines.19
Str u ctu r e of Com p ou n d 3
There are still only a few other CpNi complexes with
intramolecular coordination to the Ni center from a side
group attached to the Cp ring: for example, [η5:η2-
2,3,4,5-tetramethyl-1-(4-pentenyl)cyclopentadienyl]bro-
monickel(II).22 The overall quality of the structure of
3 (Figure 2) suffers somewhat from a dynamic disorder
of the (dimethylamino)ethyl moiety, as indicated by the
large anisotropic displacement parameters of C(6) and
C(7). This dynamic disorder in the solid state is in full
agreement with the conformative flexibility observed by
solution NMR.
The Ni-I and Ni-C(1‚‚‚5) bond lengths are within
the expected range. The coordination of the Cp ring is
distinctly off-center with the Ni closest to C(5). The
Ni-N distance of 196.0(5) pm resembles a comparably
short dative amine-Ni(II) bond, which typically range
from 200 to 220 pm, depending on the coordination
number of the Ni atom.23 The angle N-Ni-I of 103.3-
(2)° is at the upper end of the range for the bond angles
L-Ni-X of Cp(L)Ni-X compounds found from 78° 24 to
Str u ctu r e of Com p ou n d 6
The single-crystal X-ray diffraction study of 6 (Figure
3) unambiguously proves the presence of an intramo-
lecular Lewis base adduct in the solid state. The
structure of 6 also confirms the presence of a direct,
rather short Ni-In bond of 241.80(7) pm. Ni-In bond
lengths range up to 280 pm for hexacoordinate indium.25
The sum of the covalent radii and the Ni-In distance
in intermetallic alloys (e.g. ꢀ-NiIn) is around 260 pm, a
value which is also found for (η5-C5H5)(CO)Ni-In[(CH2)3-
NMe2]2 (259.8(1) pm), with a pentacoordinate indium
atom.24 Short σ(Ni-In) distances were found for lower
(23) (a) Leung, W.-P.; Lee, H.-K.; Zhou, Z.-Y.; Mak, T. C. W. J .
Organomet. Chem. 1993, 462, 7. (b) Bell, N. A.; Glockling, F.; McGregor,
A.; Schneider, M. L.; Shearer, H. M. M. Acta Crystallogr., Sect. C 1984,
40, 623.
(24) Fischer, R. A.; Herdtweck, E.; Priermeier, T. Inorg. Chem. 1994,
33, 934-943.
(25) Demartin, F.; Iapalucci, M. C.; Longoni, G. Inorg. Chem. 1993,
32, 5536.
(18) Behringer, K. D.; Blu¨mel, J . Magn. Reson. Chem. 1995, 33, 729.
(19) Blu¨mel, J .; Hofmann, P.; Ko¨hler, F. H. Magn. Reson. Chem.
1993, 31, 2.
(20) Doll, K.-H.; Pro¨ssdorf, W. J . Organomet. Chem. 1982, 224, 341.
(21) Ko¨hler, F. H.; Doll, K.-H.; Pro¨ssdorf, W. Angew. Chem., Int. Ed.
Engl. 1980, 19, 479.
(22) Lehmkuhl, H.; Naser, J . J .; Mehler, G. G.; Keil, T. T.; Danowski,
F.; Benn, R.; Mynot, R.; Schroth, G.; Gabor, B.; Kru¨ger, C.; Betz, P.
Chem. Ber. 1991, 124, 441.
(26) Weiss, J .; Stetzkamp, D.; Nuber, B.; Fischer, R. A.; Boehme,
C.; Frenking, G. Angew. Chem., Int. Ed. Engl., in press.

5752 Organometallics, Vol. 15, No. 26, 1996
Fischer et al.
seen by the torsion angles I(2)-In-Ni-P of 44.54(4)°
and I(1)-In-Ni-P of 87.46(4)°, which show that the
Ni-In bond vector is not coplanar with the bisector of
the angle I(1)-In-I(2). Also, the angle P-Ni-In of
94.39(4)° is slightly smaller than the analogous angle
of (η5-C5H5)(Ph3P)NisInBr2(OdPPh3) of 98.7(1)°. The
In-N distance of 233.2(4) pm and the Ni-P distance of
211.6(1) pm are normal.
Con clu sion s
In summary, it was shown that the [2-(dimethylami-
no)ethyl]cyclopentadienyl ligand is capable of forming
two types of intramolecular Lewis-base adducts with
electron-deficient metal centers. Either an adjacent
electron-deficient metal center can be stabilized by
bridging the metal-element bond, e.g. the Ni-In bonds
of 6-8, or the nickel center itself is complexed by the
amine function, as exemplified by 3. Compound 3 is
thought to be an interesting starting material for CO-
ligand-free, “all-hydrocarbon” (i.e. only C, H, N, and
metal atoms3) single-source precursors for OMCVD of
nickel alloy thin films, e.g. NiGa, NiIn, NiSi, NiGe, etc.
Complex 3 has the potential of a rich chemistry with
low-coordinated CpNi compounds, exemplified by com-
pound 9. In particular, the presence of the labile
intramolecular Lewis acid/base adduct (whose proper-
ties can be altered by variation of the N-CH3 groups)
and the nickel-iodide bond, which can be functionalized
in various ways as shown, should present interesting
opportunities for organonickel chemistry, such as inser-
tion reaction, bridging function, and access to different
novel neutral, anionic, and cationic compounds.
F igu r e 3. Molecular structure of 6 in the solid state
(PLATON drawing; the thermal ellipsoids are represented
at a 50% probability level). Hydrogen atoms are omitted
for clarity.
coordinated indium centers without steric repulsions
and bearing electronegative halide substituents.13 The
Ni-In bond of 6 compares to those in the compounds
(η5-C5H5)(CO)Ni-InBr2(NC7H13) of 246.3(1) pm,13a [(η5-
C5H5)(CO)Ni-InBr3][HNC7H13] of 243.7(2) pm,13a and
(η5-C5H5)(Ph3P)Ni-InBr2(OdPPh3) of 244.7(9) pm.13b
From these comparisons it is clear that the intramo-
lecular bridge exerts only a small influence on the Ni-
In bond. Also, it follows that the Ni-In bond length is
not affected by a change from CO to PR3 as supporting
ligands at the Ni center or by the type of Lewis base
ligand at the In atom. The conformative flexibility of
the aminoethyl side group allows an almost stress-free
intramolecular complexation of the indium center,
which is shown by a comparably normal deviation of
C(4) from the best Cp-ring plane of 21 pm away from
the Ni atom and is best reflected by the central
coordination of the Cp ring. The center of gravity of
the Cp ring and the atoms P, Ni, and In are almost
coplanar. The indium center is coordinated tetrahe-
drally without unusual distortions. The effect of the
intramolecular Lewis base adduct formation on the
relative orientation of the two metal fragments can be
Ack n ow led gm en t. We wish to thank the Alexander
von Humboldt Foundation (fellowship for S.N.) and the
“Fonds der Chemischen Industrie” for generous support.
Su p p or tin g In for m a tion Ava ila ble: Tables of crystal-
lographic parameters, positional parameters, thermal param-
eters, interatomic distances, and bond angles for 3 and 6 (12
pages). Ordering information is given on any current mast-
head page.
OM960712R