Stereochemistry of mono- and dinuclear complexes of rhodium, iridium and ruthenium bearing bis(diphenylphosphinomethyl)phenylphosphine

Article abstract of DOI:10.1016/S0022-328X(03)00096-2

Reaction of [Cp^*MCl₂]₂ (1a: M=Rh and 1b: M=Ir) or [(C₆Me₆)RuCl₂]₂ (1c) with bis(diphenylphosphinomethyl)phenylphosphine (dpmp) in the presence of KPF₆ generated mono- or dinuclear complexes [Cp^*RhCl(dpmp)](PF₆) (2a), [(C₆Me₆) RuCl(dpmp)](PF₆) (5c), [Cp^*MCl₂(dpmp)MClCp^*] (PF₆) (3a: M=Rh and 4b: M=Ir) or [(C₆Me₆)RuCl₂ (dpmp)RuCl(C₆Me₆)](PF₆) (6c), depending on reaction conditions. These complexes have two chiral centers and the diastereomers were separated and characterized by spectrometry and X-ray analyses. A diastereomer 2a(A) was treated with AuCl(C₄H₈S), generating a hetero-tetranuclear complex [{Cp^*RhCl₂(dpmp)Au}₂] (PF₆)₂ (7a), whereas similar reactions of 5c gave dinuclear complex [(C₆Me₆)RuCl(dpmp)AuCl] (PF₆) (8c(A)).

Full text of DOI:10.1016/S0022-328X(03)00096-2

Journal of Organometallic Chemistry 671 (2003) 8Á12
/
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Short communication
Stereochemistry of mono- and dinuclear complexes of rhodium,
iridium and ruthenium bearing
bis(diphenylphosphinomethyl)phenylphosphine
Yosuke Kosaka a, Yuichi Shinozaki a, Yoshihiro Tsutsumi a, Yoshihiro Kaburagi a,
Yasuhiro Yamamoto a,*, Yusuke Sunada b, Kazuyuki Tatsumi b,1
a Faculty of Science, Department of Chemistry, Toho University, Miyama 2-2-1, Funabashi, Chiba 274-8510, Japan
b Department of Chemistry, Research Center for Materials Science, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya
454-8602, Japan
Received 17 December 2002; received in revised form 15 January 2003; accepted 21 January 2003
Abstract
Reaction of [Cp*MCl2]2 (1a: Mꢀ
sphine (dpmp) in the presence of KPF6 generated mono- or dinuclear complexes [Cp*RhCl(dpmp)](PF6) (2a), [(C6Me6)R-
uCl(dpmp)](PF6) (5c), [Cp*MCl2(dpmp)MClCp*](PF6) (3a: MꢀRh and 4b: MꢀIr) or [(C6Me6)RuCl2(dpmp)RuCl(C6Me6)](PF6)
/
Rh and 1b: Mꢀ
/
Ir) or [(C6Me6)RuCl2]2 (1c) with bis(diphenylphosphinomethyl)phenylpho-
/
/
(6c), depending on reaction conditions. These complexes have two chiral centers and the diastereomers were separated and
characterized by spectrometry and X-ray analyses. A diastereomer 2a(A) was treated with AuCl(C4H8S), generating a hetero-
tetranuclear complex [{Cp*RhCl2(dpmp)Au}2](PF6)2 (7a), whereas similar reactions of 5c gave dinuclear complex [(C6Me6)R-
uCl(dpmp)AuCl](PF6) (8c(A)).
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Pentamethylcyclopentadienyl(rhodium or iridium); (Arene)ruthenium; Bis(diphenylphosphinomethyl)phenylphosphine; Stereochemistry
Triphosphine, especially bis(diphenylphosphino-
methyl)phenylphosphine (dpmp), plays an important
role as backbone of the construction of polynuclear
clusters. A review on its chemistry of rhodium, iridium
and gold has been sited by Balch [1]. We have developed
systematic syntheses of homo- and hetero-trimetallic
platinum and palladium clusters with tridentate phos-
phine and isocyanide ligands [2]. These complexes are
constructed fundamentally by square planar framework
and contain dpmp, carbon monoxide, halogens and
isocyanides as ligands. Recently, the self-assembled
supramolecules with pentamethylcyclopentadienyl or
cyclopentadienyl groups have been reported by several
groups [3]. Recently, we have reported preparation of
supramolecular complexes based on quasi-octahedral
geometries of rhodium(III) and iridium(III) bearing
pentamethylcyclopentadienyl ligand [4]. This type of
complexes can lead to compounds with diverse dimen-
sionality, in comparison with square planar complexes.
Chemistry on interaction between dpmp and octahedral
complexes has attracted our attention. In regard with
supramolecules, we were interested in the preparation of
polymetallic compounds bearing dpmp and penta-
methylcyclopentadienyl (or arenes) ligands, in which
the chemistry has not been developed yet. We report the
preparation and stereochemistry of mono- and dinuclear
complexes of rhodium(III), iridium(III) and rutheniu-
m(II) bearing dpmp and pentamethylcyclopentadienyl
ligands.
Reactions of [Cp*RhCl2]2 (1a) with dpmp in the
presence of KPF6 generated mono- and dinuclear
complexes [Cp*RhCl(dpmp)](PF6) (2a) [5] and
* Corresponding author. Tel.: ꢂ
1855.
E-mail
Yamamoto), i45100a@nucc.cc.nagoya-u.ac.jp (K. Tatsumi).
/
81-474-72-5076; fax: ꢂ
/
81-474-75-
addresses:
yamamoto@chem.sci.toho-u.ac.jp (Y.
ꢁ
[Cp2Rh2Cl3(dpmp)](PF6) (3a) [5], respectively, depend-
1
Fax: ꢂ81-52-789-2943.
/
ing on the reaction conditions (Scheme 1). Each of these
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00096-2

Y. Kosaka et al. / Journal of Organometallic Chemistry 671 (2003) 8Á
/12
9
Scheme 1.
complexes consists of two sets of isomers (A and B)
separated by successive recrystallization. On the basis of
1H-NMR spectrum, the reaction mixture of 2a consists
of an intensity ratio of 2:1 for A:B. The 1H-NMR
spectrum of 2a(A) showed a triplet at d 1.74 for Cp*
This molecule has two chiral centers. Since the priority
order of the ligands is Cp*ꢀClꢀ
P1ꢀP2 for the Rh
C2 for the central P2 atom,
/
/
/
center and Rhꢀ
/
Phꢀ
/
C1ꢀ
/
where C1 and C2 is the methylene carbon atoms between
P1 and P2 atoms and between P2 and P3 atoms,
protons. The 31P{1H}-NMR spectrum showed three
respectively, complex 2a(A) is an RRhSPÁ/SRhRP pair.
2
24.3 (d, JP3P2
resonances at d ꢃ
/
ꢀ
/
81.0 Hz, P3), ꢃ
105.0 Hz, JP2P3
/
9.84
Thus 2a(B) is assumed to be an RRhRPÁSRhSP pair.
/
1
(ddd, JRhP2
2
118.0 Hz, JP2P1
2
ꢀ
/
ꢀ
/
ꢀ
/
Complex 3a consists of a population of 1.1:1.0 for
3a(A) and 3a(B). The 1H-NMR spectrum of 3a(A)
showed a doublet at d 1.28 and a triplet at d 1.55 for
Cp* protons. The 31P{1H}-NMR spectrum showed
1
3.11 (dd, JP1Rh
81.0 Hz, P2) and ꢃ
/
ꢀ/115.5 Hz,
2JP1P2 105.0 Hz, P1) for the dpmp ligand. The 1H-
NMR spectrum of 2a(B) showed a triplet at d 1.78 for
ꢀ
/
Cp* protons. The 31P{1H}-NMR spectrum showed
1
three resonances at d ꢃ
/
10.0 (dt, JRh1P2ꢀ2
/
JP2P1
ꢀ
/
2
42.0 Hz, P3),
100.0 Hz,
5.00 (dd, JP1Rh 116.5
100.0 Hz, P1). The X-ray analysis of 2a(A)
2
104.5 Hz, JP2P3
1
ꢀ
/
55.0 Hz, P2), ꢃ
104.5 Hz, P1) and ꢃ
55.0 Hz, P3). The 1H-NMR
/
2.57 (dd, JP1Rh1
ꢀ
/
three resonances at d ꢃ
/
31.1 (d, JP3P2
ꢀ
/
1
2
2
ꢃ
/
9.93 (ddd, JRhP2
ꢀ
/
112.5 Hz, JP2P1
ꢀ
/
114.5 Hz, and JP1P2
ꢀ
/
/28.1 (dd,
2JP2P3
ꢀ
/
42.0 Hz, P2) and ꢃ
/
ꢀ
/
1
1JP3Rh2
ꢀ
/
144.5 Hz, 2JP3P2
ꢀ
/
2
Hz, JP1P2
ꢀ
/
spectrum of 3a(B) showed a doublet at d 1.27 and a
triplet at d 1.73 for Cp* protons. The 31P{1H}-NMR
revealed that an Rh atom is connected by terminal and
central P atoms and another P atom is free (Fig. 1) [6].
spectrum showed three resonances at d ꢃ
/
13.3 (ddd,
53.5 Hz,
105.5 Hz,
53.5 Hz,
2
2
105.5 Hz, JP2P3
1JP2Rh
P2), ꢃ
P1) and ꢃ
ꢀ
/
110.5 Hz, JP2P1
ꢀ
/
ꢀ
ꢀ
ꢀ
/
1
2
/10.1 (dd, JP1Rh
ꢀ
/
115.5 Hz, JP1P2
/
/
30.1 (dd, 1JP3Rh
ꢀ
/
145.0 Hz, 2JP3P2
/
P3). The X-ray analysis of 3a(B) revealed that an Rh
atom is connected by terminal and central P atoms and
another Rh atom is coordinated to another terminal P
atom (Fig. 2) [7]. This molecule has two chiral centers.
Since the priority order of the ligands is Cp*ꢀ
P1ꢀP2 for the Rh center and Rhꢀ C2ꢀC1 for
Phꢀ
the central P2 atom, complex 3a(B) is an RRhSPÁ
SRhRP
SRhSP pair. The geome-
/
Clꢀ
/
/
/
/
/
/
pair. Thus 3a(A) is an RRhRPÁ
/
tries around Rh and P2 atoms were found to be similar
for 2a(A) and 3a(A), and for 2a(B) and 3a(B). No
isomerization from 2a(A) (3a(A)) to 2a(B) (3a(B)) and
its reverse reaction occurred at room temperature. No
reaction of 2a(A) with xylyl isocyanide occurred.
Fig. 1. Molecular structure of 2a(A). A PF6 was omitted for clarity.
˚
Selected bond lengths (A) and angles (8): Rh(1)ꢀ
/
Cl(1), 2.389(3);
P(2), 2.338(3); Cl(1)ꢀRh(1)ꢀP(1),
P(2), 85.0(1); P(1)ꢀRh(1)ꢀP(2), 71.6(1).
Rh(1)ꢀ
83.9(1); Cl(1)ꢀ
/
P(1), 2.303(3); Rh(1)ꢀ
/
/
/
/
Rh(1)ꢀ
/
/
/

10
Y. Kosaka et al. / Journal of Organometallic Chemistry 671 (2003) 8Á12
/
(4b(A)) and yellow (4b(B)) ones having the formula of
ꢁ
[Cp2Ir2Cl3(dpmp)](PF6) under various reaction condi-
tions, without producing any mono-nuclear complexes
1
[5]. Population of 4b(A) and 4b(B) is 1:1.1. In the H-
NMR spectra, Cp* protons showed a doublet at d 1.27
and a triplet at d 1.56 for 4b(A) and a doublet at d 1.27
and a triplet at d 1.79 for 4b(B). No isomerization was
observed standing for 120 h, whereas the treatment of
4b(B) with xylyl isocyanide led to an isomerization to
4b(A), almost quantitatively, suggesting that 4b(A) is
superior in stability to 4b(B) (Eq. (1)). Metallacycle
containing the Rh atom showed to be more stable than
that containing the Ir atom.
4b(B)04b(A)
(1)
The X-ray analysis of 4b(A) revealed that the struc-
ture is essentially similar to that of rhodium analog
3a(B), and the difference is whether each of Cl atom and
P2-phenyl group is located on the opposite side for the
former or on the same side for the latter. The molecular
structure of 4b(A) is depicted in Fig. 3 [8].
Reaction of [(C6Me6)RuCl2]2 (1c) with dpmp was
carried out in the presence of KPF6, generating mono-
and dinuclear complexes [(C6Me6)RuCl(dpmp)](PF6)
(5c) and [(C6Me6)2Ru2Cl3(dpmp)](PF6) (6c), respec-
tively, depending on reaction conditions [5]. These
complexes consist of two diastereomers and the popula-
tion is 2:1 for 5c(A):5c(B) and 1:1.3 for 6c(A):6c(B). In
the 1H-NMR spectra, the methyl protons appeared at d
1.94 for 5c(A) and at d 2.06 for 5c(B). X-ray analysis of
5c(A) revealed to be a similar geometry to 2a(A). The
1H-NMR spectrum of 6c(A) showed two singlets at d
1.63 and 1.97 for methyl protons. The 31P{1H}-NMR
Fig. 2. Molecular structure of 3a(B). A PF6 anion was omitted for
˚
clarity. Selected bond lengths (A) and angles (8): Rh(1)ꢀ
/Cl(1),
2.420(2); Rh(1)ꢀ
2.375(2); Rh(2)ꢀP(2), 2.314(2); Rh(2)ꢀ
Cl(2), 91.67(7); Cl(1)ꢀRh(1)ꢀP(1), 88.64(5); Cl(2)ꢀ
89.93(6); Rh(1)ꢀP(1)ꢀC(51), 106.9(2); P(1)ꢀC(51)ꢀP(2), 129.9(3);
Cl(3)ꢀRh(2)ꢀP(2), 86.02(5); Cl(3)ꢀRh(2)ꢀP(3), 86.58(6); P(2)ꢀ
Rh(2)ꢀP(3), 72.28(5); Rh(2)ꢀP(3)ꢀC(52), 95.1(2); P(2)ꢀC(52)ꢀP(3),
95.783; Rh(2)ꢀP(2)ꢀC(52), 94.8(2).
/
Cl(2), 2.425; Rh(1)ꢀ
/
P(1), 2.335(2); Rh(2)ꢀ
P(3), 2.305(2); Cl(1)ꢀ
Rh(1)ꢀ
/
Cl(3),
/
/
/
Rh(1)ꢀ
/
/
/
/
/P(1),
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
Complex 2a(A) or 2a(B) was treated with 1a at room
temperature, exclusively generating 3a(A) or 3a(B),
respectively. Complex 3a(A) or 3a(B) was treated with
dpmp in a similar way, affording 2a(A) or 2a(B),
respectively. In these reactions, the conversion from
2a(B) to 3a(B) and its reverse reaction are slower than
inter-conversion between 2a(A) and 3a(A). These reac-
tions proceeded stereospecifically.
When [Cp*IrCl2]2 (1b) reacted with dpmp in the
presence of KPF6, isolable complexes were orange
spectrum showed three resonances at d ꢃ
/
5.41 (dd,
0.07 (d,
2
50.0 Hz, JP2P3
2JP2P1
ꢀ
/
ꢀ
/
92.0 Hz, P2), ꢃ
/
˚
Fig. 3. Molecular structure of 4b(A). The PF6 anions were omitted for clarity. Selected bond lengths (A) and angles (8): Ir(1)ꢀ
/
Cl(1), 2.389(3); Ir(1)ꢀ
/
P(1), 2.299(3); Ir(1)ꢀ
/
P(2), 2.318(3); Ir(2)ꢀ
/
Cl(2), 2.408(3); Ir(2)ꢀ
/
Cl(3), 2.430(4); Ir(2)ꢀ
/
P(3), 2.311; Cl(1)ꢀ
/
Ir(1)ꢀ
/
P(1), 85.7(1); Cl(1)ꢀIr(1)ꢀP(2),
/
/
87.6(1); P(1)ꢀIr(1)ꢀP(2), 72.2(1); Cl(2)ꢀ
/
/
/
Ir(2)ꢀ
/
Cl(3), 89.0(1); Cl(2)ꢀ
/
Ir(2)ꢀP(3), 88.9(1).
/

Y. Kosaka et al. / Journal of Organometallic Chemistry 671 (2003) 8Á
/12
11
Scheme 2.
2
2JP3P2
ꢀ
/
92.0 Hz, P1) and ꢃ
/
29.3 (d, JP1P2
ꢀ
/
50.0 Hz,
found for complexes bearing Auꢀ
/
Au bonds [10Á
/
12], the
P3) for the dpmp ligand. The 1H-NMR spectrum of
6c(B) showed two singlets at d 1.63 and 1.82 for methyl
protons. The 31P{1H}-NMR spectrum showed three
weak interaction between two Au atoms is assumed to
be present. Each Cp*RhCl2 moiety is connected by an
outer P1 atom of the dpmp ligand. The molecule also
2
2
has two chiral centers of P2 and P2*, with an RP2SP2*
Á
/
resonances at d ꢃ
50.0 Hz, P2), ꢃ2.16 (d, 2JP1P2
(d, 2JP3P2 50.0 Hz, P3). No isomerization proceeded in
the absence and presence of xylyl isocyanide, suggesting
the strong RuꢀP bond.
/
0.49 (dd, JP2P1
ꢀ
/
88.5 Hz, JP2P3
ꢀ
/
88.5 Hz, P1) and ꢃ
/
27.1
SP2RP2* pair. It was confirmed by the X-ray analysis of
8c(A) that the AuCl group coordinated to the free
terminal P atom of 2a(A) and its stereochemistry was
/
ꢀ
/
ꢀ
/
remained to be an RRÁSS pair [13].
/
/
The research on the mechanism and reactions of those
complexes is now in progress.
Reactions of 2a(A) or 5c(A) with AuCl(C4H8S) were
carried out, generating [{Cp*RhCl2(dpmp)Au}2](PF6)2
(7a) or [(C6Me6)RuCl(dpmp)AuCl](PF6) (8c(A)), respec-
tively (Scheme 2) [5]. X-ray analysis of 7a revealed that
the molecule has a crystallographically imposed inver-
sion center in the middle of the AuÁ Á ÁAu* vector (Fig. 4)
1. Supplementary materials
˚
Spectral data and elementary analyses for all new
compounds, an ORTEP of 8c(A), and X-ray analyses data
(anisotropic thermal parameters, bond lengths and bond
angles) for 2a(A), 3a(B), 4b(A), 7a and 8c(A) are
available. The CCDC numbers of these complexes are
190354, 190353, 202043, 190356 and 202044 for 2a(A),
3a(B), 4b(A), 7a and 8c(A).
[9]. Although an AuÁ Á ÁAu separation of 3.203(2) A is
˚
3.15 A
slightly long in comparison with those of 2.95Á
/
References
[1] A.P. Balch, in: L.H. Pignolet (Ed.), Homogeneous Catalysis with
Metal Phosphine Complexes, Plenum Press, New York, 1983, p.
167 and references therein.
[2] T. Tanase, Y. Yamamoto, Trends Organomet. Chem. 3 (1999) 35
and references therein.
[3] (a) K.K. Klausmeyer, T.B. Rauchfuss, S.R. Wilson, Angew.
Chem. 110 (1808) 1998;
(b) K.K. Klausmeyer, T.B. Rauchfuss, S.R. Wilson, Angew.
Chem. Int. Ed. 37 (1998) 1694;
(c) S.M. Contakes, K.K. Klausmeyer, R.M. Milberg, S.R.
Wilson, T.B. Rauchfuss, Organometallics 17 (1998) 3633;
(d) D.J. Darensbourg, W.-Z. Lee, M.J. Adams, D.L. Larkins,
J.H. Reibenspies, Inorg. Chem. 38 (1999) 1378;
(e) S.M. Contakes, K.K. Klausmeyer, T.B. Rauchfuss, Inorg.
Chem. 39 (2000) 2069.
Fig. 4. Molecular structure of 7a. The PF6 anions were omitted for
˚
clarity. Selected bond lengths (A) and angles (8): Auꢀ
AuꢀP(3), 2.297(4); RhꢀCl(1), 2.432(5); RhꢀCl(2), 2.417(3); Rhꢀ
2.326(4); P(2)ꢀAuꢀP(3), 164.6(1); Cl(1)ꢀRhꢀCl(2), 91.8(2); Cl(1)Rhꢀ
P(1), 87.3(2); Cl(2)ꢀRh(1)ꢀP(1), 88.1(2).
/
P(2), 2.336(4);
[4] (a) H. Suzuki, N. Tajima, K. Tatsumi, Y. Yamamoto, Chem.
Commun. (2000) 1801.;
/
/
/
/P(1),
/
/
/
/
/
(b) Y. Yamamoto, H. Suzuki, N. Tajima, K. Tatsumi, Chem. Eur.
J. 8 (2002) 372.
/
/

12
Y. Kosaka et al. / Journal of Organometallic Chemistry 671 (2003) 8Á
/12
[5] All new complexes were identified by their elemental analyses and
spectroscopic data, which are reported in supplementary materi-
[9] Crystal data for 7a: C84H88P8Cl4F12Au2Rh2CH2Cl2, monoclinic,
˚
˚
space group P21/n (no. 14), aꢀ
/
13.430(6) A, bꢀ
/
13.59(1) A, cꢀ
/
3
˚
˚
als.
[6] Crystal data for 2a(A): C42H44P4ClF6Rh, monoclinic, space group
24.670(5) A, bꢀ
cmꢃ3, Rꢀ
0.065 and Rwꢀ
tions [I ꢀ2.0s(I)] with 505 variables at 278. The structure was
/
95.53(3)8, Vꢀ
/
4480(3) A , Zꢀ
/
2, rcalc
ꢀ
/
1.716 g
/
/
0.106 [wꢀ
/
1/s2(Fo)] for 4487 reflec-
˚
3
˚
˚
P21/n (no. 14), aꢀ
bꢀ103.74(2)8, Vꢀ
0.155, Rwꢀ0.207 [wꢀ
variables and R1ꢀ0.074 for 4155 reflections [I ꢀ
/
12.487(4) A, bꢀ
/
22.640(5) A, cꢀ
/
15.395(6) A,
/
˚
/
/
4227(2) A , Zꢀ
/
4, rcalc
ꢀ/
1.453 g cmꢃ3, Rꢀ
/
solved by Patterson methods and refined by full-matrix least-
squares techniques using the TEXSAN program package [14].
[10] A.L. Balch, V.J. Catalano, B.C. Noll, M.M. Olmstead, J. Am.
Chem. Soc. 112 (1990) 7558.
/
/
1/s2(Fo)] for 7404 reflections with 482
/
/
2.0s(I)]. The
measurement was made by Rigaku AFC5S. The structure was
solved by Patterson methods (DIRDIF92) and refined by full-
matrix least-squares techniques using the TEXSAN program
package [14].
[11] A.L. Balch, E.Y. Fung, M.M. Olmstead, J. Am. Chem. Soc. 112
(1990) 5181.
[12] H. Schmidbauer, A. Wohlleben, U. Schubert, A. Frank, G.
Huttner, Chem. Ber. 110 (1977) 2751.
[7] Crystal data for 3a(B): C53H61P4Cl5F6Rh2, monoclinic, space
˚
˚
group P21/c (no. 14), aꢀ
/
11.518(2) A, bꢀ
/
25.566(2) A, cꢀ
/
[13] Crystal data for 8c(A):
C
45H49Cl8P4F6OAuRu, Mꢀ1283.6,
/
3
˚
˚
19.254(4) A, bꢀ
g cmꢃ3, Rꢀ
0.088, Rwꢀ
with 631 variables and R1ꢀ
/
94.95(2)8, Vꢀ
0.134 [wꢀ
0.045 for 6391 reflections [I ꢀ
/5648(1) A , Zꢀ
/
4, rcalc 1.478
ꢀ
/
˚
monoclinic, space group C2/c (no. 15), aꢀ
/
22.123(3) A, bꢀ
/
/
/
/
1/s2(Fo)] for 9939 reflections
3
˚
˚
˚
12.8859(4) A, cꢀ
Zꢀ8, Dꢀ
1.794 g cmꢃ3, mꢀ
5056 and Tꢀ293 K. Data were collected on a MSC/ADSC
/
35.639(1) A, bꢀ
/
110.663(2)8, Vꢀ
/9506(1) A ,
/
/
/
/
/
38.30 cmꢃ1 (MoÁ
/
Ka), F(0 0 0)ꢀ
/
2.0s(I)]. The measurement was made by QuantumCCD/Rigaku
AFC7 at 208. The structure was solved by Patterson methods
(DIRDIF92) and refined by full-matrix least-squares techniques
using the TEXSAN program package [14].
/
QuantumCCD/Rigaku AFC7. The structure was solved by direct
methods and non-hydrogen atoms were refined anisotropically
using full-matrix least-squares based on F to give R1ꢀ
/
0.046 and
[8] Crystal data for 4b(A): C52H59P4Cl3F6Ir2, monoclinic, space
˚
˚
Rwꢀ0.073 for 7619 reflections. The ORTEP appears in the
/
group P21/c (no. 14), aꢀ
/
15.367(2) A, bꢀ
/
12.1256(5) A, cꢀ
/
3
˚
˚
supplementary materials. The structure was solved by Patterson
methods and refined by full-matrix least-squares techniques using
the TEXSAN program package [14].
28.1703(9) A, bꢀ
1.793 g cmꢃ3, Rꢀ
reflections [I ꢀ3.0s(I)] with 604 variables. The measurement was
/
94.345(2)8, Vꢀ
/
5233.9(6) A , Zꢀ
/
4, rcalc
ꢀ
/
/
0.052 and Rwꢀ
/
0.098 [wꢀ
1/s2(Fo)] for 8913
/
/
made by QuantumCCD/Rigaku AFC7 at 208. The structure was
solved by Patterson methods and refined by full-matrix least-
squares techniques using the TEXSAN program package [14].
[14] TEXSAN: Crystal Structure Analysis Package, Molecular Structure
Corporation Houston, TX, 1985 and 1992.