Quasi-octahedral complexes of pentamethylcyclopenta-dienyliridium(III) bearing bis(diphenylphosphinomethyl)phenylphosphine (dpmp)

Article abstract of DOI:10.1039/b411045p

Reaction of [Cp*IrCl₂]₂ (1) with dpmp in the presence of KPF₆ afforded a binuclear complex [Cp*IrCl(dpmp-P¹,P²;P³)IrCl ₂Cp*](PF₆) (2) (dpmp = (Ph₂PCH ₂)₂PPh). The mononuclear complex [Cp*IrCl(dpmp-P¹,P²)](PF₆) (4) was generated by the reaction of [Cp*IrCl₂(BDMPP)] (BDMPP = PPh{2,6-(MeO)₂C₆H₃}₂) with dpmp in the presence of KPF₆. These mono- and binuclear complexes have four-membered ring structures with a terminal and a central P atom of the dpmp ligand coordinated to an iridium atom as a bidentate ligand. Since there are two chiral centers at the Ir atom and a central P² atom, there are two diastereomers that were characterized by spectrometry. Complexes anti-4 and syn-4 reacted with [Cp*RhCl₂]₂ or [(C ₆Me₆)RuCl₂]₂, giving the corresponding mixed-metal complexes, anti- and syn-[Cp*IrCl(dppm-P ¹,P²;P³)MCl₂L](PF₆) (6: M = Rh, L = Cp*; 7: M = Ru, L = C₆Me₆). Treatment with AuCl(SC₄H₈) gave tetranuclear complexes, anti- and syn-8 [{Cp*IrCl(dppm-P¹,P²;P³)AuCl} ₂](PF₆)₂ bearing an Au-Au bond. Reaction of anti-4 with PtCl₂(cod) generated the trinuclear complex anti-9, anti-[{Cp*IrCl(dppm-P¹,P²;P³)} ₂PtCl₂](PF₆)₂. These reactions proceeded stereospecifically. The P,O-chelated complex syn-[Cp*IrCl(BDMPP-P,O)] (syn-10) (BDMPP-P,O = PPh{2,6-(MeO) ₂C₆H₃}{2-O-6-(MeO)C₆H ₃}₂) reacted with dpmp in the presence of KPF ₆, generating the corresponding anti-complex as a main product as well as a small amount of syn-complex, [Cp*Ir(BDMPP-P,O)(dppm-P ¹)](PF₆) (11). The reaction proceeded preferentially with inversion. The reaction processes were investigated by PM3 calculation, anti-11 was treated with MCl₂(cod), giving anti-[Cp*Ir(BDMPP-P,O)(dppm-P¹;P²,P ³)MCl₂](PF₆) (14: M = Pt; 15: M = Pd), in which the MCl₂ moiety coordinated to the two free P atoms of anti-11. The X-ray analyses of syn-2, anti-2, anti-4, anti-8 and anti-11 were performed.

Full text of DOI:10.1039/b411045p

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F U L L P A P E R
Quasi-octahedral complexes of pentamethylcyclopenta-
dienyliridium(III) bearing bis(diphenylphosphinomethyl)-
phenylphosphine (dpmp)
Yasuhiro Yamamoto,*a,b Yosuke Kosaka,b Yoshihiro Tsutsumi,b Yusuke Sunada,c
Kazuyuki Tatsumi,c Takei Fumiea and Takahashi Shigetoshia
a
The Institute of Scientific and Industrial Research, Osaka University, Mihogaoka, Ibaraki,
Osaka, 567-0047, Japan. E-mail: yamamo24@sanken.osaka-u.ac.jp
Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba,
b
274-8510, Japan. E-mail: yamamoto@chem.sci.toho-u.ac.jp
Research Center for Materials Science and Department of Chemistry,
c
Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya,
454-8602, Japan. E-mail: i45100a@nucc.cc.nagoya-u.ac.jp
Received 19th July 2004, Accepted 2nd August 2004
First published as an Advance Article on the web 19th August 2004
Reaction of [Cp*IrCl2]2 (1) with dpmp in the presence of KPF6 afforded a binuclear complex [Cp*IrCl(dpmp-
P1,P2;P3)IrCl2Cp*](PF6) (2) (dpmp = (Ph2PCH2)2PPh). The mononuclear complex [Cp*IrCl(dpmp-P1,P2)](PF6)
(4) was generated by the reaction of [Cp*IrCl2(BDMPP)] (BDMPP = PPh{2,6-(MeO)2C6H3}2) with dpmp in the
presence of KPF6. These mono- and binuclear complexes have four-membered ring structures with a terminal and a
central P atom of the dpmp ligand coordinated to an iridium atom as a bidentate ligand. Since there are two chiral
centers at the Ir atom and a central P2 atom, there are two diastereomers that were characterized by spectrometry.
Complexes anti-4 and syn-4 reacted with [Cp*RhCl2]2 or [(C6Me6)RuCl2]2, giving the corresponding mixed-metal
complexes, anti- and syn-[Cp*IrCl(dppm-P1,P2;P3)MCl2L](PF6) (6: M = Rh, L = Cp*; 7: M = Ru, L = C6Me6).
Treatment with AuCl(SC4H8) gave tetranuclear complexes, anti- and syn-8 [{Cp*IrCl(dppm-P1,P2;P3)AuCl}2](PF6)2
bearing an Au–Au bond. Reaction of anti-4 with PtCl2(cod) generated the trinuclear complex anti-9, anti-
[{Cp*IrCl(dppm-P1,P2;P3)}2PtCl2](PF6)2. These reactions proceeded stereospecifically. The P,O-chelated complex
syn-[Cp*IrCl(BDMPP-P,O)] (syn-10) (BDMPP-P,O = PPh{2,6-(MeO)2C6H3}{2-O-6-(MeO)C6H3}2) reacted
with dpmp in the presence of KPF6, generating the corresponding anti-complex as a main product as well as a
small amount of syn-complex, [Cp*Ir(BDMPP-P,O)(dppm-P1)](PF6) (11). The reaction proceeded preferentially
with inversion. The reaction processes were investigated by PM3 calculation. anti-11 was treated with MCl2(cod),
giving anti-[Cp*Ir(BDMPP-P,O)(dppm-P1;P2,P3)MCl2](PF6) (14: M = Pt; 15: M = Pd), in which the MCl2 moiety
coordinated to the two free P atoms of anti-11. The X-ray analyses of syn-2, anti-2, anti-4, anti-8 and anti-11 were
performed.
We extended the chemistry of rhodium and ruthenium com-
Introduction
plexes to that of the iridium complexes. Here we report the
preparations of mono- and binuclear iridium complexes and
their transformation to heteronuclear complexes. We also wish
to describe the reactions of the iridium complex bearing P,O-
coordination with dpmp. Its stereochemistry was discussed by
PM3 calculation.
The bis(diphenylphosphinomethyl)phenylphosphine (dpmp)
ligand can construct mono-, bi-, tri- and polynuclear complexes
by versatile bridging and chelating coordination behaviors.1
The chemistry has been limited to four- or two-coordination
complexes containing rhodium, iridium, gold and silver atoms.
We have systematically explored the chemistry of palladium and
platinum bearing dpmp and isocyanide ligands and the prepara-
tions of homo- and hetero-polynuclear complexes based on their
palladium and platinum complexes.2 These complexes bearing
the dpmp ligand have been essentially constructed by the square
planar frameworks.
The six-fold bonding capability of the octahedral unit leads
to complexes with diverse dimensionality, in comparison with
those that are square planar. We were interested in the chem-
istry of the interaction between quasi-octahedral complexes
and dpmp because of the expectation of various coordina-
tion behaviors and polynuclear complexes. Previously we have
reported that the reactions of [Cp*RhCl2]2 (Cp* = C5Me5) or
[(arene)RuCl2]2 (arene = p-cymene, C6Me6) with dpmp in the
presence of KPF6 generated mono- and binuclear complexes
containing four-membered rings deriving from coordination
of a terminal P atom and a central P atom of the dpmp ligand
to the metal atoms.3–5 These complexes consist of two diaste-
reomers, anti-form and syn-form,6 because of the presence of
two chiral centers at the metal atom and a central P atom of the
dpmp ligand.
Experimental
All reactions were carried out under a nitrogen atmosphere.
Dichloromethane was distilled over CaH2 and diethyl
ether was distilled over LiAlH4. [Cp*IrCl2]2 (1),7 xylyl iso-
cyanide (XylNC),8 (Ph2PCH2)2PPh (dpmp),9 AuCl(SC4H8),10
[Pd(XylNC)4](PF6)2 (Xyl = 2,6-Me2C6H3),11 Cp*IrCl2[PPh2{2,6-
(MeO)2C6H3}] (3a),12 [Cp*IrCl2(BDMPP-P)] (BDMPP-
P = PPh{2,6-(MeO)2C6H3}2) (3b),12 Cp*IrCl2(TDMPP-P) (3c)
(TDMPP-P = P{2,6-(MeO)2C6H3}3),12
P,OMe)](PF6)12 (BDMPP-P,OMe = PPh{2,6-(MeO)2C6H3}{2-
O-6-MeOC6H3}), (syn-10)
syn-Cp*IrCl(BDMPP-P,O)12
[Cp*IrCl(BDMPP-
(BDMPP-P,O = PPh{2,6-(MeO)2C6H3}{2-O-6-MeOC6H3})
were prepared according to the literature. Infrared spectra were
recorded on FT/IR-5300 or Perkin Elmer system 2000FT-IR
spectrometer. The UV-vis spectra were measured on a U-best30
instrument. NMR spectra were recorded on JEOL JNM-ECL-
400, JEOL JNM-ECL-600 or Bruker ARX-400 spectrometers.
The 1H NMR spectra were measured at 400 or 600 MHz. The
31P{1H} NMR spectra were measured at 161 MHz using 85%
T h i s j o u r n a l i s
©
T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 4
D a l t o n T r a n s . , 2 0 0 4 , 2 9 6 9 – 2 9 7 8
2 9 6 9

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H3PO4 as an external reference. The FAB mass spectra were
measured on a JEOL MX300 spectrometer.
molar ratio of anti-4 and syn-4 is ca 3:1. Each diastereomer was
separated by successive recrystallization. UV/Vis (CH2Cl2): kmax
335 nm. IR (Nujol): 837 cm−1 (PF6). FAB mass: m/z 869 ([M+])
(M = ionic molecule). Calc. for C42H44ClF6IrP4: C 49.73, H 4.37.
Found: C 49.25, H 4.35%. anti-form: 1H NMR (CDCl3): d 1.76
Preparation of [Cp*IrCl(dpmp-P1,P2;P3)IrCl2Cp*](PF6) (2)
(a) From 1, dpmp and KPF6. A mixture of 1 (80.7 mg,
0.101 mmol), dpmp (58.6 mg, 0.116 mmol) and KPF6 (35.9 mg,
0.195 mmol) was stirred in acetone (5 mL) and CH2Cl2 (5 mL)
for 14 h at room temperature. The solvent was removed and the
residue was extracted with CH2Cl2. The solution was concen-
trated to ca 1 mL and diethyl ether was added to the solution,
affording a mixture of orange and yellow diastereomers
(127.0 mg, 44.5%). The separation of the mixture was carried
out by successive recrystallization from CH2Cl2 and diethyl
ether. In a separate experiment, 1H NMR spectrum of the reac-
tion mixture was measured and the molar ratio between anti-2
and syn-2 is 1:1.1. UV/Vis (CH2Cl2): kmax 335 nm; IR (Nujol):
837 cm−1 (PF6). anti-2 (orange yellow): 1H NMR (CDCl3): d 1.26
(d, JHP = 2.5 Hz, Cp*, 15H), 1.56 (t, JHP = JHP = 2.5 Hz, Cp*,
2
(t, JHP1 = JHP1 = 2.5 Hz, Cp*, 15H), 3.44 (dt, JHH = 16.8 Hz,
2JHP = 2JHP = 14.0 Hz, CH2, 1H), 3.47 (dt, 2JHH = 16.8 Hz, 2JHP
2JHP = 14.0 Hz, CH2, 1H), 4.28 (dt, 2JHH = 16.0 Hz, 2JHP = 2JHP
=
=
12.8 Hz, CH2, 1H), 5.71 (dt, 2JHH = 16.0 Hz, 2JHP = 2JHP = 9.2 Hz,
CH2, 1H), 6.75–7.7 (m, Ph, 25H). 31P{1H} NMR (CDCl3):
2
2
d −44.7 (dd, JP2P1 = 65.5 Hz, JP2P3 = 85.0 Hz, P2), −36.4 (d,
2JP1P2 = 65.5 Hz, P1), −25.3 (d, 2JP3P2 = 85.0 Hz, P3), −143.6 (sep.,
1JPF = 707.5 Hz, PF6). syn-form (17.3%): H NMR (CDCl3): d
1
1.81 (t, JHP1 = JHP2 = 2.5 Hz, Cp*, 15H), 3.12 (dd, 2JHH = 15.0 Hz,
2JHP = 9.0 Hz, CH2, 1H), 3.29 (dd, 2JHH = 15.0 Hz, 2JHP = 7.0 Hz,
CH2, 1H), 4.38 (q, 2JHH = 2JHP = 2JHP = 13.0 Hz, CH2, 1H), 6.32
(dt, 2JHH = 13.0, 2JHP = 2JHP = 8.5 Hz, CH2, 1H), 6.9–7.6 (c, Ph,
25H). 31P{1H} NMR (CDCl3): d −44.0 (d, JP2P1 = 61.5 Hz,
2
2JP2P3 = 51.5 Hz, P2), −38.5 (d, JP1P2 = 61.5 Hz, P1), −31.6 (d,
2
2
2
15H), 4.02 (dd, JHH = 2JHP = 11.5 Hz, JHP = 28.5 Hz, CH2,
2JP3P2 = 51.5 Hz, P3), −143.6 (sep., 1JPF = 707.5 Hz, PF6).
Similarly, a mixture of anti- and syn-4 was also obtained from
the substitution reaction of [Cp*IrCl(BDMPP-P,OMe)](PF6)
with dpmp.
2
2
2
1H), 4.29 (dd, JHH = 11.5 Hz, JHP = 5.0 Hz, JHP = 16.5 Hz,
CH2, 1H), 5.17 (dt, JHH = 16.0 Hz, JHP = 2JHP = 8.0 Hz, CH2,
2
2
1H), 5.56 (dt, JHH = 16.0 Hz, JHP = 2JHP = 10.0 Hz, CH2,
2
2
1H), 6.9–8.1 (m, Ph, 25H). 31P{1H} NMR (CDCl3): d −50.8
(dd, JP2P1 = 63.0 Hz, JP2P3 = 51.0 Hz, P2), −34.6 (d, JP1P2
=
=
1
2
2
Preparation of [Cp*Ir(dpmp)](OTf)2 (5)
63.0 Hz, P1), −5.04 (d, 2JP3P2 = 51.0 Hz, P3), −143.6 (sep., 1JPF
1
707.5 Hz, PF6). syn-2 (yellow): H NMR (CDCl3): d 1.27 (d,
From 4. To a solution of 4 (18.6 mg, 0.0132 mmol) and dpmp
(9.9 mg, 0.196 mmol) in acetone (5 mL) and CH2Cl2 (5 mL)
AgOTf (90 mg, 0.035 mmol) was added at room temperature.
After the solution was stirred for 5 h, the pale yellow solution
was concentrated to dryness and the residue was extracted with
CH2Cl2. After removal of the solvent, the residue was washed
with diethyl ether and recrystallized from CH2Cl2 and diethyl
ether, giving pale yellow crystals (18.0 mg, 60.2%) of 5.
JHP = 2.5 Hz, Cp*, 15H), 1.79 (t, JHP = JHP = 2.5 Hz, Cp*,
2
2
15H), 4.04 (dd, JHH = 2JHP = 13.5 Hz, JHP = 28.5 Hz, CH2,
1H), 4.29 (dt, 2JHH = 13.5 Hz, 2JHP = 2JHP = 10.0 Hz, CH2, 1H),
4.43 (dt, JHH = 16.0 Hz, JHP = 2JHP = 7.0 Hz, CH2, 1H), 4.67
(dt, 2JHH = 16.0 Hz, 2JHP = 2JHP = 8.0 Hz, CH2, 1H), 6.9–8.1 (m,
Ph, 25H). 31P{1H} NMR (CDCl3): d −50.0 (dd, 1JP2P3 = 50.5 Hz,
2
2
2JP2P1 = 65.0 Hz, P2), −42.8 (d, JP1P2 = 65.0 Hz, P1), −2.56 (d,
2
2JP3P2 = 50.5 Hz, P3), −143.6 (sep., JPF = 707.5 Hz, PF6). Calc.
1
for C52H59Cl3F6Ir2P4·0.5CH2Cl2: C 43.33, H 4.16. Found: C
43.52, H 4.10%.
(a) From 1 and dpmp. A mixture of 1 (54.7 mg, 0.069 mmol),
dpmp (89.0 mg, 0.176 mmol) and AgOTf (62.6 mg, 0.244 mmol)
was stirred in acetone (5 mL) and CH2Cl2 (10 mL) at room tem-
perature. After 12 h, the solvent was removed and the residue was
washed with diethyl ether and extracted with CH2Cl2. The solu-
tion was concentrated to ca. 2 mL and diethyl ether was added,
affording pale yellow crystals (102.5 mg, 65.6%) of 5. FAB
mass: m/z 982 ([M + OTf]+, 10%), 832 ([M]+, 100%) (M = ionic
molecule). 1H NMR (CDCl3): d 1.71 (q, JHP = 2.5 Hz, Cp*, 15H),
5.85 (m, CH2, 2H), 6.38 (m, CH2, 2H), 7.3–8.4 (m, Ph, 25H). The
31P{1H} NMR (CDCl3): d −92.5 (t, 2JPP = 69.0 Hz, P2), −55.0 (d,
2JP3P2 = 69.0 Hz, P1,P3). Calc. for C44H44F6IrO6P3S2: C, 46.68; H,
3.92. Found: C, 45.89; H, 3.87%.
(b) From 4 and 1. A mixture of anti-4 and syn-4 (molar ratio of
ca. 1.3:1) (30.0 mg, 0.0296 mmol), and 1 (12.2 mg, 0.015 mmol)
was stirred in CH2Cl2 (10 mL) at room temperature for 10 h
at room temperature. The solvent was removed under reduced
pressure and the residue was washed with diethyl ether. The
1H NMR spectrum of the residue (reaction mixture) showed
the molar ratio of ca. 1.4:1 for anti-2 and syn-2. The reddish
brown solid was recrystallized from CH2Cl2 and diethyl ether,
affording orange yellow crystals of a mixture of anti-2 and syn-2
(17.8 mg, 42.6%).
Isomerization from syn-2 to anti-2
Preparation of [Cp*IrCl(dpmp-P1,P2;P3)RhCl2Cp*](PF6) (6)
A mixture of syn-2 (38.2 mg, 0.027 mmol) and xylyl isocyanide
(20.0 mg, 0.152 mmol) was stirred in CH2Cl2 (5 mL) and acetone
(5 mL) at room temperature. After 25 h, the solvent was removed
and the residue was recrystallized from CH2Cl2 and diethyl ether,
affording anti-2 (29.7 mg, 77.8%).
A mixture of anti-4 (18.3 mg, 0.018 mol) and [Cp*RhCl2]2
(5.6 mg, 0.010 mmol) was stirred in CH2Cl2 (10 mL) for 5 h.
After the solution was concentrated to ca. 1 mL, diethyl ether
was added, affording reddish orange crystals (13.8 mg, 58.0%)
of anti-6. UV/Vis (CH2Cl2): kmax 406, 234 nm. IR (Nujol):
839 cm−1 (PF6). FAB mass: m/z 1179 ([M]+) (M = ionic
Preparation of [Cp*IrCl(dpmp-P1,P2)](PF6) (4)
1
molecule). anti-6: H NMR (CDCl3): d 1.27 (d, JHP = 2.5 Hz,
(a) From Cp*IrCl2(BDMPP-P) 3b. A mixture of 3b (41.3 mg,
0.0573mmol), dpmp(50.0mg, 0.0987mmol)andKPF6 (29.6mg,
0.161 mmol) in acetone (5 mL) and CH2Cl2 (5 mL) was stirred at
room temperature for 17 h. After the solvent was removed, the
residue was washed with diethyl ether. The 1H NMR spectrum
of the residue showed the molar ratio of ca 1.6:1 for anti-4 and
syn-4. The residue was extracted with CH2Cl2. The solution was
concentrated to ca. 2 mL and diethyl ether was added, affording
pale yellow solids of anti- and syn-4 (35.7 mg, 61.4%).
Cp*, 15H), 1.54 (t, JHP = JHP = 2.5 Hz, Cp*, 15H), 4.08 (dd,
2
2
2JHH = 12.5 Hz, JHP = 28.0 Hz, CH2, 1H), 4.22 (dt, JHH
=
=
2
2
2
12.5 Hz, JHP = JHP = 10.0 Hz, CH2, 1H), 5.05 (dt, JHH
8.0 Hz, 2JHP = 2JHP = 16.0 Hz, CH2, 1H), 5.54 (dt, 2JHH = 8.0 Hz,
2JHP = 2JHP = 16.0 Hz, CH2, 1H), 6.9–8.2 (m, Ph, 25H). 31P{1H}
2
2
NMR (CDCl3): d −49.5 (dd, JP2P3 = 55.0 Hz, JP2P1 = 62.0 Hz,
P2), −34.6 (d, JP1P2 = 62.0 Hz, P1), 26.2 (dd, JP3P2 = 55.0 Hz,
1JRhP = 143.0 Hz, P3), −143.6 (sep., 1JPF = 707.5 Hz, PF6).
Similarly, a mixture of 6 consisting of ca. 1.5:1 molar ratio
for anti- and syn-forms was obtained from the reaction of 4
(anti:syn = ca. 1.5:1) with [Cp*RhCl2]2. syn-6 (17.3%): 1H NMR
2
2
(b) From [Cp*IrCl2(TDMPP-P)] 3c. Similarly, 4 (76.9 mg,
68.3%) was prepared from 3c (83.3 mg, 0.111 mmol), dpmp
(85.2 mg, 0.168 mmol) and KPF6 (52.3 mg, 0.284 mmol). The
(CDCl3): d 1.27 (d, JHP3 = 4.0 Hz, Cp*, 15H), 1.78 (t, JHP1 = JHP2
=
2.5 Hz, Cp*, 15H), 4.02 (dt, JHH = 16.0 Hz, JHP = JHP = 11.0 Hz,
2 9 7 0
D a l t o n T r a n s . , 2 0 0 4 , 2 9 6 9 – 2 9 7 8

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CH2, 1H), 4.18 (dt, JHH = 16.0 Hz, JHP = JHP = 11.0 Hz, CH2,
affording yellow crystals of anti-9 (16.0 mg, 56.7%). UV/Vis
2
2
1
1H), 4.34 (dt, JHH = 14.0 Hz, JHP = 2JHP = 8.0 Hz, CH2, 1H),
(CH2Cl2): kmax 328 nm. IR (Nujol): 839 cm−1 (PF6). H NMR
4.60 (dt, 2JHH = 16.0 Hz, 2JHP = 2JHP = 8.0 Hz, CH2, 1H), 6.9–8.5
(CD2Cl2): d 1.56 (t, JHP = 2.5 Hz, Cp*, 30H), ca. 2.95 (m, CH2,
2H), ca. 4.30 (m, CH2, 2H), ca. 4.98 (m, CH2, 4H), 6.8–7.6 (m,
Ph, 50H). 31P{1H} NMR (CD2Cl2): d −50.5 (dd, 2JP2P3 = 48.5 Hz,
2
(m, Ph, 25H). 31P{1H} NMR (CDCl3): d −48.4 (dd, JP2P3
=
53.0 Hz, JP2P1 = 65.0 Hz, P2), −42.8 (d, JP1P2 = 65.0 Hz, P1),
2
2
28.5 (dd, JP3P2 = 53.0 Hz, JRhP3 = 144.5 Hz, P3), −143.6 (sep.,
1JPF = 707.5 Hz, PF6). Calc. for C52H59Cl3F6IrP4Rh·0.5CH2Cl2:
C, 46.17; H, 4.43. Found: C, 46.48; H, 4.49%.
2JP2P1 = 58.5 Hz, P2), −34.2 (d, JP1P2 = 58.5 Hz, P1), 5.14 (d,
2
1
2
1
1
2JP3P2 = 48.5 Hz, JP3Pt = 3763.4 Hz, P3), −143.6 (sep., JPF
=
707.5 Hz, PF6). Calc. for C84H88Cl4F12Ir2P8Pt: C, 43.97; H, 3.87.
Found: C, 43.64; H, 3.92%.
Preparation of [Cp*IrCl(dpmp-P1,P2;P3)RuCl2(C6Me6)](PF6) (7)
Preparation of [Cp*Ir(BDMPP-P,O)(dpmp-P1)](PF6) (11)
Similarly to the preparation of 6, reddish orange crystals of 7
(17.2 mg, 64.7%) were prepared from a mixture of anti-4 and
syn-4 (20.0 mg, 0.020 mmol) consisting of ca. 2.4:1 molar ratio
and [(C6Me6)RuCl2]2 (6.7 mg, 0.010 mmol). On the basis of the
NMR spectrum, 7 showed the presence of diastereomers in ca.
2.5:1 molar ratio for anti-form:syn-form. The separation of two
diastereomers was not performed. UV/Vis (CH2Cl2): kmax 338,
296 nm. IR (Nujol): 839 cm−1 (PF6). anti-7: 1H NMR (CDCl3):
d 1.53 (t, JHP1 = JHP2 = 2.5 Hz, Cp*, 15H), 1.65 (s, C6Me6, 18H),
3.8 (m, CH2, 2H), 4.90 (dt, 2JHH = 16.0 Hz, 2JHP1 = 2JHP2 = 8.0 Hz,
A mixture of syn-10 (50.0 mg, 0.068 mmol), dpmp (39.0 mg,
0.077 mmol) and KPF6 (45.0 mg, 0.245 mmol) was stirred in
acetone (10 mL) and CH2Cl2 (5 mL) at room temperature.
After 24 h, the solvent was removed under reduced pressure
and the residue was extracted with CH2Cl2. The solvent was
dried and the residue was washed with diethyl ether, afford-
ing pale yellow solid (58.9 mg, 64%) of anti-11. The 31P{1H}
NMR spectrum of the residue was measured and showed the
presence of diastereomers consisting of ca. 23:molar ratio.
Isolation of pure syn-11 was unsuccessful because of small
formation ratio. FAB mass: m/z 1201 ([M − 1]+) (M = cationic
part). UV/Vis (CH2Cl2): kmax 303 nm. IR (Nujol): 1581, 1554
(P,O-chelate), 839 (PF6). anti-11: 1H NMR (CDCl3): d 1.15 (t,
JHP = 2.2 Hz, Cp*, 15H), 3.06 (s, CH3O, 3H), 3.16 (s, CH3O,
3H), 3.45 (s, CH3O, 3H), 6.3–8.1 (c, CH2 + aromatic H,
CH2, 1H), 5.51 (dt, JHH = 16.0 Hz, JHP = 2JHP = 8.0 Hz, CH2,
1H), 6.8–8.2 (m, Ph, 25H). 31P{1H} NMR (CDCl3): d −49.1 (dd,
1JP2P1 = 63.0 Hz, 2JP2P3 = 52.5 Hz, P2), −35.5 (d, 2JP1P2 = 63.0 Hz,
P1), 26.1 (d, 2JP3P2 = 52.5 Hz, P3), −143.6 (sep., 1JPF = 707.5 Hz,
PF6). syn-7: 1H NMR (CDCl3): d 1.64 (s, C6Me6, 18H), 1.72 (t,
JHP1 = JHP2 = 2.5 Hz, Cp*, 15H), 4.0 (m, CH2, 3H), 4.38 (dt,
2
2
2
2
2JHH = 16.0 Hz, JHP1 = 2JHP2 = 8.0 Hz, CH2, 1H), 6.9–8.3 (m,
44H). 31P{1H} NMR (CDCl3): d −35.2 (dd, JP2P3 = 124.5 Hz,
Ph, 25H). 31P{1H} NMR (CDCl3): d −49.6 (dd, 2JP2P1 = 63.5 Hz,
2JP2P1 = 25.8 Hz, P2), −23.3 (d, JP3P2 = 124.5 Hz, P3), −6.80
2
2
2
2JP2P3 = 51.5 Hz, P2), −43.0 (d, JP1P2 = 63.5 Hz, P1), 28.5 (d,
(dd, JP1P2 = 25.8 Hz, JP1P0 = 20.4 Hz, P1), 10.1 (d, JP0P1
=
1
1
2JP3P2 = 51.5 Hz, P3), −143.6 (sep., JPF = 707.5 Hz, PF6). Calc.
20.4 Hz, P0), −143.6 (sep, JPF = 707.5 Hz, PF6). syn-11: H
NMR (CDCl3): d 1.07 (t, JHP = 2.2 Hz, Cp*, 15H), 3.26 (s,
CH3O, 3H), 3.31 (s, CH3O, 3H), 3.57 (s, CH3O, 3H), 6.3–8.1
(c, CH2 + aromatic H, 44H). 31P{1H} NMR (CDCl3): d −36.7
for C54H62Cl3F6IrP4Ru·0.5CH2Cl2: C, 47.06; H, 4.56. Found: C,
47.43; H, 4.61%.
Preparation of [{Cp*Ir(dpmp-P1,P2;P3)AuCl}2](PF6)2 (8)
(dd, JP2P3 = 135.2 Hz, JP2P1 = 29.0 Hz, P2), −23.9 (d, JP3P2 =
2
2
2
2
135.2 Hz, P3), −5.74 (dd, JP1P2 = 29.0 Hz, JP1P0 = 22.0 Hz,
P1), 7.36 (d, 2JP0P1 = 22.0 Hz, P0), −143.6 (sep, JPF = 707.5 Hz,
PF6). Calc. for C63H64F6IrO4P5: C, 56.21; H, 4.79. Found: C,
55.64, H, 4.83%.
A solution of 4 (20.4 mg, 0.020 mmol; anti-: syn- = ca. 1.3:1)
and AuCl(SC4H8) (7.4 mg, 0.023 mmol) in CH2Cl2 (10 mL) was
stirred at room temperature for 14 h. The solvent was removed
to dryness and the residue was washed with diethyl ether,
followed by recrystallization from CH2Cl2 and diethyl ether
to give orange crystals of 8 (13.4 mg, 53.8%). The molar ratio
of anti-8 and syn-8 is ca. 1.3:1. Diastereomers were separated
by successive recrystallization from CH2Cl2 and diethyl ether.
UV/Vis (CH2Cl2): kmax 335 nm. IR (Nujol): 837 cm−1 (PF6). FAB
Preparation of [CpIr(BDMPP-P,O)(dpmp-P1;P2,P3)PtCl2]
(anti-14)
A mixture of anti-11 (37.8 mg, 0.028 mmol) and PtCl2(cod)
(6.0 mg, 0.016 mmol) was stirred in acetone (10 mL) at room
temperature for 24 h. After the solvent was removed and the
residue was washed with diethyl ether, the yellow solid was
recrystallized from CH2Cl2 and diethyl ether, affording yellow
crystals of anti-14 (28.9 mg, 64.0%). Fluorescence X-ray
1
mass: m/z 1100 ([(M/2) − 1]+) (M = ionic molecule). anti-8: H
NMR (CDCl3): d 1.67 (t, JHP1 = JHP2 = 2.5 Hz, Cp*, 15H), 3.79
2
2
2
(dd, JHH = 15.5 Hz, JHP = 6.0 Hz, JHP = 13.0 Hz, CH2, 1H),
4.22 (dt, JHH = 15.5 Hz, JHP = 2JHP = 9.5 Hz, CH2, 1H), 4.79
2
2
2
2
1
(dt, JHH = 15.5 Hz, JHP = 2JHP = 12.5 Hz, CH2, 1H), 6.23 (dt,
analysis: Ir:Pt:Cl:P:F = 1:0.9:1.8:5:7. H NMR (CDCl3):
2JHH = 15.5 Hz, 2JHP = 2JHP = 9.5 Hz, CH2, 1H), 6.8–7.8 (m, Ph,
d 1.20 (t, JHP = 2.0 Hz, Cp*, 15H), 3.20 (s, CH3O, 3H), 3.33
(s, CH3O, 3H), 3.50 (s, CH3O, 3H), 6–8.0 (c, CH2 + Ph, 32H).
Calc. for C63H64Cl2F6IrO4P5Pt: C, 46.93; H, 4.00. Found: C,
47.14; H, 3.95%.
25H). 31P{1H} NMR (CDCl3): d −51.7 (dd, JP2P3 = 21.0 Hz,
2
2JP2P1 = 54.0 Hz, P2), −31.3 (d, JP1P2 = 54.0 Hz, P1), 17.7 (d,
2
2JP3P2 = 21.0 Hz, P3), −143.6 (sep., 1JPF = 707.5 Hz, PF6). syn-8:
1H NMR (CDCl3): d 1.85 (t, JHP1 = JHP1 = 2.5 Hz, Cp*, 15H),
3.33 (dt, JHH = 15.5 Hz, JHP = 2JHP = 8.0 Hz, CH2, 1H), 4.06
(ddd, 2JHH = 15.5 Hz, 2JHP = 7.5 Hz, 2JHP = 13.0 Hz, CH2, 1H),
4.68 (dt, 2JHH = 16.0 Hz, 2JHP = 2JHP = 12.5 Hz, CH2, 1H), 7.00
Preparation of [CpIr(BDMPP-P,O)(dpmp-P1;P2,P3)PdCl2](PF6)
(anti-15)
2
2
A mixture of anti-14 (47 mg, 0.035 mmol) and PdCl2(cod)
(7.1 mg, 0.025 mmol) was stirred in acetone (10 mL) at
room temperature. After 6 h, the solvent was removed and
the residue was washed with diethyl ether to give yellow
solids (47.3 mg, 88.7%). Recrystallization of the residue from
CH2Cl2 and diethyl ether gave pure yellow crystals of anti-15.
1H NMR (CDCl3): d 1.30 (t, JHP = 2.0 Hz, Cp*, 15H), 3.05 (s,
OMe, 3H), 3.15 (s, OMe, 3H), 3.44 (s, OMe, 3H), 6.2–8.1 (c,
CH2 + aromatic H, 44H). 31P{1H} NMR (CDCl3): d −5.85 (br,
2
2
(dt, JHH = 16.0 Hz, JHP = 2JHP = 9.5 Hz, CH2, 1H), 6.9–8.0
(m, Ph, 25H). 31P{1H} NMR (CDCl3): d −47.6 (dd, JP2P3
=
2
15.0 Hz, JP2P1 = 57.5 Hz, P2), −37.3 (d, JP1P2 = 57.5 Hz, P1),
2
2
16.9 (d, JP3P2 = 15.0 Hz, P3), −143.6 (sep., JPF = 707.5 Hz,
PF6). Calc. for C42H44AuCl2F6IrP4: C, 40.46; H, 3.56. Found: C,
40.27; H, 3.59%.
2
1
Preparation of [{Cp*IrCl(dpmp-P1,P2P3)}2(PtCl2)](PF6)2 (anti-9)
2
2
A mixture of anti-4 (25 mg, 0.0246 mmol) and PtCl2(cod)
(4.8 mg, 0.128 mmol) was stirred in CH2Cl2 (5 mL) at room
temperature for 24 h. After the solvent was removed under
reduced pressure, the residue was washed with hexane and
diethyl ether and recrystallized from CH2Cl2 and diethyl ether,
P3), 13.1 (d, JP0P1 = 17.5 Hz, P0), 14.7 (dd, JP1P2 = 6.5 Hz,
2JP1P0 = 17.5 Hz, P1), 16.0 (dd, JP2P1 = 6.5 Hz, JP2P3 = 25.5
Hz, P2), −144.3 (sep, JPF = 702.5 Hz, PF6). Calc. for C63H6
2
2
1
4Cl2F6IrO4P5Pd·CH2Cl2: C, 47.79; H, 4.14. Found: C, 47.94;
H, 4.29%.
D a l t o n T r a n s . , 2 0 0 4 , 2 9 6 9 – 2 9 7 8
2 9 7 1

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Preparation of [{CpIr(BDMPP-P,O)(dpmp-P1;P2,P3)}2{trans-
Pd(XylNC)2}](PF6) (anti-16)
all reflections measured in the range 3.0 < 2h < 50°. The intensity
images were measured at 0.5° intervals of x for a duration of
20 s. The frame data were integrated using a d*TREK program
package, and the data sets were corrected for absorption using
a REQAB program. The crystal parameters along with data
collections are summarized in Table 1. The data were corrected
for Lorenz and polarization effects. Atomic scattering factors
were taken from the usual tabulation of Cromer and Waber.13
Anomalous dispersion effects were included in Fc;14 the
values of f and f were those of Creagh and McAuley.15 All
calculations were performed using the teXsan crystallographic
software package.16
Similarly to the preparation of anti-15, yellow crystals
(38.1 mg, 79.4%) of anti-16 was prepared from anti-11 (39 mg,
0.029 mmol) and [Pd(XylNC)4](PF6)2 (15 mg, 0.016 mmol) in
CH2Cl2 (10 mL). IR (Nujol): 2198 (NC), 1583, 1555 (P,O-
1
chelation), 841 (PF6) cm−1. H NMR (CDCl3): d 1.82 (t, JHP
=
2.0 Hz, Cp*, 30H), 1.86 (s, o-Me, 12H), 3.20 (s, CH3O, 6H), 3.33
(s, CH3O, 6H), 3.50 (s, CH3O, 6H), 6–8.0 (c, CH2 + Ph, 70H).
Calc. for C144H146F24Ir2N2O8P12Pd: C, 51.61; H, 4.39; N, 0.84.
Found: C, 51.76; H, 4.40; N, 0.60%.
Reactions of syn-10 with Lewis bases
Determination of the structures
A representative preparation is shown as follows.
All structures were solved by Patterson methods (DIRDIF94
PATTY). The position of all non-hydrogen atoms except the
pentamethylcyclopentadienyl groups for syn-2 and anti-11, and
two phenyl groups of the dpmp ligand for anti-8 refined isotropi-
cally, were refined with anisotropic thermal parameters by using
full-matrix least-squares based on F values. All hydrogen atoms
except a hydrogen atom for each of the methyl protons of the
pentamethylcyclopentadienyl groups were calculated at the ideal
positions with the C–H distance of 0.97 Å. The positions of
non-hydrogen atoms of anti-13b and syn-13b were refined aniso-
tropically using full-matrix least-squares based on F2 values. All
hydrogen atom positions were introduced at the ideal positions
and were refined using a riding model (SHELXL-97).17
A mixture of syn-10 (60 mg, 0.082 mmol) and Lewis base
(ca. 0.090 mol) and KPF6 (ca. 0.20 mmol) was stirred for 5 h at
room temperature. After the solvent was removed, the residue
was washed with diethyl ether and hexane and extracted with
CH2Cl2. The solution was concentrated and the residue was
recrystallized from CH2Cl2, benzene and diethyl ether, or
CH2Cl2 and diethyl ether, affording two kinds of yellow and
pale yellow crystals (cubic and column shapes), formulated as
1
[Cp*Ir(BDMPP-P,O)(L)](PF6) 13. 13a (L = PPh3; 74.6%): H
NMR (CDCl3): d 1.19 (t, JPH = JPH = 2.0 Hz, Cp*)a, 1.35 (t,
JPH = JPH = 2.0 Hz, Cp*)s, 2.72 (s, MeO, 3H)a, 2.89 (s, MeO, 3H)a,
3.02 (s, MeO, 3H)s, 3.15 (s, MeO, 3H)s, 3.33 (s, MeO, 3H)s, 4.02
(s, MeO, 3H)a, 5.7–7.8 (c, Ph, 26H)a + s 31P{1H} NMR (CDCl3):
.
CCDC reference numbers 242126 (anti-2), 232309 (syn-2),
232310 (anti-4), 232311 (8) and 232312 (anti-11).
See http://www.rsc.org/suppdata/dt/b4/b411045p/ for crystal-
lographic data in CIF or other electronic format.
d 15.4 (d, JP0P = 19.0 Hz, P0)a, −3.07 (s, P0)s, −6.77 (d, JP0P
19.0 Hz, P)a, −10.4 (d, JP0P = 21.0 Hz, P)s and −143.5 (sep. JPF
=
=
707.5 Hz, PF)a + s). Molar ratio: anti-form:syn-form = ca. 7:3.
Calc. for C49H50IrF6O4P3: C, 53.40; H, 4.57. Found: C, 53.07; H,
4.82. 13b (L = P(C6H4-p-Me)3; 89.4% yield): 1H NMR (CDCl3): d
1.18 (t, JHP0 = JHP1 = 2.0 Hz)a, 1.34 (t, JHP0 = JHP1 = 2.0 Hz)s, 2.31
(bs, p-Me, 9H)a + s, 2.70 (s, OMe, 3H)a, 2.89 (s, OMe, 3H)a, 3.02 (s,
OMe, 3H)s, 3.14 (s, OMe, 3H)s, 3.35 (s, OMe, 3H)s, 4.10 (s, OMe,
3H)a, 5.7–7.7 (c, aromatic, 23H). 31P{1H} NMR (CDCl3): d 15.6
(d, JPP = 19.3 Hz, PL)a, −2.96 (d, JPP = 20.9 Hz, PL)s, −8.30 (d,
JPP = 19.3 Hz, P)a, −11.9 (d, JPP = 20.9 Hz, PL)b and −143.5 (sep.
JPF = 707.5 Hz, PF)a + s. Molar ratio: anti-form:syn-form = ca.
7.3:2.7. Calc. for C52H56IrF6O4P3: C, 54.56; H, 4.93. Found: C,
54.30; H, 5.04%. 13c (L = pyrazine; 83.5%): 1H NMR (CDCl3):
d 1.51 (d, JPH = 2.0 Hz, Cp*)a, 1.62 (JPH = 2.0 Hz, Cp*)s, 2.74 (s,
MeO, 3H)a, 3.06 (s, MeO, 3H)a, 3.95 (s, MeO, 3H)a, 5.7–8.9 (c,
pyrazine, Ph)a + s 31P{1H} NMR (CDCl3): d 9.73 (s, P)a, 9.89 (s,
P), −143.5 (sep. JPF = 707.5 Hz, PF). anti-form:syn-form = ca.
98:2. Calc.. For C35H39IrF6 N2O4P3: C, 45.70; H, 4.27; N, 3.05.
Found: C, 45.43; H, 4.33; N, 3.00%. 13d (L = XylNC; 88.3%
PM3 calculation
The PM3 calculation was performed by PC Spartan’04
Windows, Wavefunction Inc. The calculation was performed
by using the rhodium analogs as model compounds, since the
PM3 calculation for transition metals is not presently available
for Ir atom.
Results and discussion
Reactions of [Cp*IrCl2]2 (1) with dpmp
When 1 was treated with an equivalent of dpmp in the pres-
ence of KPF6 at room temperature, two kinds of orange yellow
and yellow diastereomers (2) with the empirical formula of
[Cp*2Ir2Cl3(dpmp)](PF6) were isolated by successive recrystal-
lization (Scheme 1). The presence of similar diastereomers has
been documented for rhodium(III)4 and ruthenium(II)5 com-
plexes. In a separate experiment, the 1H NMR spectrum of the
reaction mixture indicated the presence of a mixture of anti-2
and syn-2 consisting of an approximately 1:1.1 intensity ratio.
The ratio in solution remained unchanged even after a week at
room temperature. Two diastereomers are not interconvertible.
Each diastereomer could be obtained as suitable crystals for X-
ray analysis (Fig. 1). In the 1H NMR spectra, the Cp* protons
appeared at d 1.26 (d) and 1.56 (t) ppm for anti-2 and at d 1.27 (d)
and 1.76 (t) ppm for syn-2.6 The 31P{1H} NMR spectra appeared
at d −50.8 (dd), −34.6 (d) and −5.04 (d) ppm for the P2, P1 and
P3 atoms of the dpmp ligand in anti-2 in which the Cl atom and
the P2-substituted Ph group are situated at opposite sides and at
d −50.0 (dd), −42.8 (d) and −2.56 (d) ppm for those in syn-2 in
which the Cl atom and the P2-substituted Ph group are situated
at the same side. The chemical shifts of the 31P nuclei for the
iridium complexes appeared at higher magnetic fields than those
found in the rhodium analogs,4 reflecting the higher electron
density on the Ir atom than that on the Rh atom.
1
yield): IR (Nujol): 2162 (NC), 839 (PF6) cm−1. H NMR
(CDCl3): d 1.82 (d, JHH = 2.0 Hz, 15H)a, 1.86 (s, o-Me, 6H)a, 3.13
(s, OMe, 3H)a, 3.27 (s, OMe, 3H)a, 3.53 (s, OMe, 3H)a, 5.0–7.8 (c,
aromatic, 14H). 31P{1H}NMR(CDCl3):d11.4(s, P0)a and −144.3
(sep. JPF = 707.5 Hz, PF). Calc. for C40H44IrF6NO4P2: C, 49.48;
H, 4.57; N, 1.44. Found: C, 49.76; H, 4.65; N, 1.23%.
Data collection
Cell constants of syn-2, anti-13b and syn-13b were determined
from 20 reflections on a Rigaku four-circle automated diffracto-
meter, AFC5S or AFC7R. The data collection was carried out
by using the 2h–x scan method. Throughout the data collection
the intensities of the three standard reflections were measured
every 200 reflections as a check of the stability of the crystals
and no decay was observed. An absorption correction was made
with w scan methods. The measurements for anti-2, anti-4, ant-8
and anti-11 were made on a Quantum CCD/Rigaku AFC7 or
a Rigaku/MSC Mercury CCD diffractometer, using Mo-Ka
radiation at −100 °C under a cold nitrogen stream. Four pre-
liminary data frames were measured at 0.5° increments of x, in
order to assess the crystal quality and preliminary unit cell pa-
rameters were calculated. The cell parameters were refined using
When syn-2 was treated with xylyl isocyanide at room temp-
erature, an isomerization of syn-2 to anti-2 was found to occur,
but its reverse reaction did not proceed (Scheme 2). These results
2 9 7 2
D a l t o n T r a n s . , 2 0 0 4 , 2 9 6 9 – 2 9 7 8

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Scheme 1 Preparation of mono- and binuclear complexes, where MD-
MPP = PPh2{2,6-(MeO)2C6H3}, BDMPP = PPh{2,6-(MeO)2C6H3}2,
TDMPP = P{2,6-(MeO)2C6H3}3, dpmp = (Ph2PCH2)2PPh; the PF6
anion is omitted for clarity.
Fig. 1 Molecular structures of [Cp*IrCl(dpmp)IrCl2Cp*](PF6) 2:
(a) anti-2 and (b) syn-2; The PF6 anion, hydrogen atoms and solvent
molecule are omitted for clarity.
suggest that the syn-2 is formed kinetically and anti-2 is thermo-
dynamically more stable than syn-2. In the rhodium analogs,
similar reactions recovered the starting materials,4 whereas in the
ruthenium complexes the reactions cleave a Ru–P3 coordination
bond, giving (C6Me6)RuCl2(XylNC) and [(C6Me6)RuCl(dpmp-
P1,P2)](PF6) accompanied by no change of geometry.5 Thus,
the temporary metal–P bond cleavage in a four-membered ring
occurred in the syn-iridium complex, and no cleavage proceeded
for the rhodium and ruthenium complexes. The four-membered
rings for the Rh and Ru complexes are superior in stability to
that for the Ir complex.
In order to prepare mononuclear complexes, the reactions with
an excess of dpmp were carried out, the only isolated complex,
however, was the binuclear one without formation of any mono-
nuclear complex. These results showed the different reactivity
D a l t o n T r a n s . , 2 0 0 4 , 2 9 6 9 – 2 9 7 8
2 9 7 3

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Scheme 2 Isomerization of syn-2 to anti-2 and related reactions for
rhodium(III) and ruthenium(II) complexes; the PF6 anion is omitted for
clarity.
from those for the rhodium and ruthenium analogs.4,5 Mono-
nuclear complexes anti- and syn-[Cp*IrCl(dpmp-P1,P2)](PF6) (4)
could be prepared by treatment of Cp*IrCl2(MDMPP-P) (3a),
Cp*IrCl2(BDMPP-P) (3b) or Cp*IrCl2(TDMPP-P) (3c) with
dpmp in the presence of KPF6 or the substitution reaction of
[Cp*IrCl(BDMPP-P,OMe)](PF6) with dpmp (Scheme 1). Based
1
on the H NMR spectra of the reaction mixtures, the ratio of
anti-4 and syn-4 is ca. (3–1.6):1.6 Two diastereomers were sepa-
rated by successive recrystallization. The Cp* protons appeared
at d 1.76 and 1.81 ppm for anti-4 and syn-4, respectively. In the
31P{1H} NMR spectra the chelate P nuclei appeared at d ca. −44
and ca. −37 ppm, not significantly different from those found in
2, but the free P3 nucleus at d ca. −28 ppm appeared at higher
magnetic field by approximately 23 ppm than that found in 2.
A similar trend has been noted in the rhodium and ruthenium
analogs.4,5 The detailed structure was confirmed by an X-ray
analysis of anti-4 (Fig. 2). An approximately 1.3:1 mixture
of anti-4 and syn-4 reacted with 1 to give a similar (ca. 1.4:1)
ratio of anti-2 and syn-2 suggesting that this reaction proceeds
stereospecifically.
Scheme 3 Reactions of anti- or syn-4 with various metal complexes;
the PF6 anions are omitted for clarity.
complex (6) established from elemental analysis and FAB mass
spectrometry as [Cp*IrCl(dpmp-P1,P2;P3)RhCl2Cp*](PF6). The
formation ratio is approximately similar to the molar ratio of
anti- and syn-forms for the starting complex (4). The reaction
proceeded stereospecifically. Based on a separate experiment
by the reaction of anti-4 with [Cp*RhCl2]2 to give anti-6, the
Cp* protons of anti-6 appeared at d 1.26 (d) and 1.54 (t) ppm
consisting of a 1:1 intensity ratio, due to the Cp* protons co-
ordinated to the Rh atom and those to the Ir atom, respectively.
The Cp* protons for syn-6 was observed at d 1.27 (d) and 1.78
(t) ppm. The 31P{1H} NMR spectra showed three resonances
due to the P2, P1 and P3 nuclei of the dpmp ligand for each
diastereomer, which appeared at d −49.5 (dd), −34.6 (d) and
26.1 (d) ppm for anti-6, and at d −48.4 (dd), −42.8 (d) and
28.5 (d) ppm for syn-6, respectively. Similarly, a mixture of
diastereomers (4) was treated with [(C6Me6)RuCl2]2 at room
temperature, generating two reddish orange diastereomers (7),
formulated as [Cp*IrCl(dpmp- P1,P2;P3)RuCl2(C6Me6)](PF6).
1
On the basis of H NMR spectrum, this reaction also proceeds
stereospecifically. In the 1H NMR spectra, the Cp* and C6Me6
protons appeared at d 1.53 (t) and 1.65 (s) ppm for anti-7 and at
d 1.72 (t) and 1.64 (s) ppm for syn-7, respectively. In the 31P{1H}
NMR spectra, the chemical shifts of the P1 and P2 nuclei
appeared at higher magnetic fields by ca. 30 ppm than those
found in the rhodium/ruthenium analog, [Cp*RhCl(dpmp-
P1,P2,P3)RuCl2(p-cymene)](PF6), whereas those of the both P3
nuclei are similar.4
When a mixture of anti- and syn-4 was treated with an equiva-
lent of AuCl(SC4H8), the reaction readily occurred, generating a
yellow complex (8), established from elemental analysis and FAB
mass spectrometry as [Cp*IrCl(dpmp-P1,P2;P3)AuCl](PF6). The
1H NMR spectrum of the reaction mixture showed the pres-
ence of two diastereomers. The ratio is similar to that of the
starting complex (4). The Cp* protons appeared as a triplet at
d 1.67 ppm for the main product and at d 1.85 ppm for a minor
one, respectively. The 31P{1H} NMR spectra showed three reso-
nances at d −51.7 (dd), −31.3 (d) and 17.7 (d) ppm for the former
complex and at d −47.6 (dd), −37.3 (d) and 16.9 (d) ppm for the
latter one, assignable to the P2, P1 and P3 nuclei, respectively. The
X-ray analysis of the main complex revealed that the molecule
consists of a dimeric structure bearing an Au–Au bond with an
Fig. 2 Molecular structure of [Cp*IrCl(dpmp-P1,P2)](PF6) anti-4;
the PF6 anion and hydrogen atoms and solvent molecule are omitted
for clarity.
Reactions of mononuclear complex [Cp*IrCl(dpmp-P1,P2)](PF6)
(4)
In order to extract a Cl anion, 4 was treated with a large excess
of KPF6 and only the starting material was recovered. A similar
reaction with AgOTf, however, generated a pale yellow 3-
complex [Cp*Ir(dpmp-P1,P2,P3)](OTf)2 (5) bearing a tridentate
ligand as evidenced by the presence of a quartet for the Cp*
protons in the 1H NMR spectrum (Scheme 3). This complex was
also prepared by the reaction of 1 and dpmp with AgOTf.
When a mixture of anti- and syn-4 was treated with
[Cp*RhCl2]2 at room temperature, an addition reaction
occurred readily, generating a reddish orange mixed metal
2 9 7 4
D a l t o n T r a n s . , 2 0 0 4 , 2 9 6 9 – 2 9 7 8

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anti-form (Fig. 3). Thus, the minor complex is assumed to be a
syn-conformer.
Fig. 4 One independent molecular structure of [Cp*Ir(BDMPP-
P,O)(dpmp-P1)](PF6) anti-11: the PF6 anion, hydrogen atoms and
solvent molecule are omitted for clarity.
Fig. 4 showed that the complex is a RIrRP1/SIrSP1 pair, in
which the dpmp ligand and the P-substituted 2,6-dimethoxy-
phenyl group sit at the opposite side and its stereochemistry
is designated as an anti-form. Thus, the stereochemistry of the
main product is an opposite diastereomer for that of the starting
one (syn-10), suggesting that the reaction proceeded preferen-
tially with inversion.
Previously we have reported that the reaction of [Cp*IrCl2]2
or [Cp*RhCl2]2 with PPh{2,6-(MeO)2C6H3}2 (BDMPP) exclu-
sively generated the demethylated complexes, syn-10 (>98%)12
or syn-[Cp*RhCl(BDMPP-P,O)] syn-12 (>95%),18 respectively.
These results accord with the fact that syn-12 is more stable
by ~3.0 kcal mol−1 than anti-12, on the basis of the PM3 calcu-
lations for anti- and syn-12,19 suggesting that the demethylation
reaction proceeded with thermodynamic control.
Fig. 3 Molecularstructureof [{Cp*IrCl(dpmp-P1,P2;P3)AuCl}2](PF6)2
anti-8: the PF6 anions and hydrogen atoms are omitted for clarity.
Complex (anti-4) reacted readily with a planar complex
PtCl2(cod), generating the yellow complex anti-[{Cp*Ir(dpmp-
P1,P2;P3)}2(PtCl2)](PF6)2 (anti-9). The 1H NMR spectrum
showed a triplet at d 1.56 ppm for the Cp* protons, suggesting
a symmetric structure. The 31P{1H} NMR spectrum showed a
double doublet at d −50.5 ppm due to the P2 nucleus and two
doublets at d −34.2 and 5.14 ppm. Since the resonance at d
5.14 ppm accompanies the satellite peaks due to 195Pt nucleus,
it is assignable to the P3 nucleus. The molecule has a structure
in which each complex ligand coordinated to the Pt metal at
trans-positions.
The reaction of syn-10 with dpmp was found to afford
anti-11 preferentially with stereochemical inversion as above-
mentioned. In order to examine whether similar stereochemical
reactions occur in the reactions with other Lewis bases, the reac-
tions with Lewis bases such as aromatic phosphines, pyrazine,
isocyanide and amine were carried out in the presence of KPF6
and they afforded a mixture of anti- and syn-[Cp*Ir(BDMPP-
P,O)(L)](PF6) (13a: L = PPh3; 13b: L = P(p-MeC6H4)3; 13c:
L = pyrazine); 13d: L = 2,6-Me2C6H3NC (XylNC); 13e: L =
n-PrNH2). The main products were above 70% for 13a and 13b,
and above 98% for 13c, 13d, and 13e. X-Ray analyses of the
main and minor products for 13b were confirmed as anti- and
syn-conformer, respectively (Fig. 5).20 Although suitable crystals
for X-ray analyses could not be obtained for 13d and 13e, they
are assumed to be an anti-form based on the 1H NMR spectra.
Similarly to the results of 12, the syn-conformers of 13 in
all cases were calculated to be somewhat higher in stability
(0.5–3.5 kcal mol−1) compared to the corresponding anti-
conformers, as estimated by the PM3 calculations of the Rh
analogs [Cp*Rh(BDMPP-P,O)(L)](PF6).20
Preparation and reactions of [Cp*IrCl(BDMPP-P,O)(dpmp-
P1)](PF6) (11)
When syn-10,12 in which the Cl atom and the P-substituted 2,6-
(MeO)2C6H3 group sit at the same side, was treated with dpmp in
a 1:1 molar ratio in the presence of KPF6 at room temperature,
a yellow complex formulated as [Cp*Ir(BDMPP-P,O)(dpmp-
P1)](PF6) (11) was obtained on the basis of the elemental
1
analysis and the mass spectrometry (Scheme 4). The H NMR
spectrum of 11 showed the presence of two diastereomers in a
20:1 molar ratio. It was confirmed by an X-ray analysis that
the main complex has the structure that a terminal P1 atom
of the dpmp ligand coordinated to the Ir atom (Fig. 4). The
complex has two chiral centers at an Ir atom and a P0 atom of
the P,O-chelating ligand, and the priority order of the ligands
decreases with Cp* > P0chelate > P1 > O for the Ir center and Ir >
Cchelate > R (= 2,6-dimethoxyphenyl) > Ph for the P0chelate center
(Scheme 4).
On the basis of the PM3 calculation of the [Cp*Rh(BDMPP-
P,O)]+ species (R- and S-forms for the P center) assumed as
the intermediate (I) in the substitution reaction, the Cp* ring
bent to the 2,6-(MeO)2C6H3 side as calculated by the average
Cp*center–Rh–X–C (X = P or O) torsion angle of 145°. Steric
crowding of the 2,6-dimethoxyphenyl side in both intermediates
would prevent an attack of the ligand from this side leading to
the syn-conformer. This led to the preferential formation of the
anti-conformer. In these calculations, an intermediate (IR) with
the R-form showed the presence of an agostic Rh–Hortho bond
(1.661 Å) between the Rh atom and the ortho-H atom of the
phenyl group, but the phenyl side is still kept open in comparison
with the 2,6-dimethoxyphenyl side (Fig. 6). On the other hand,
the phenyl side of the other intermediate (IS) with the S-form is
completely free around the metal atom. Thus, a nucleophile was
Scheme 4 Reactions of syn-10 with dpmp and Lewis bases, where
P^P^P = dpmp and R = 2,6-(MeO)2C6H3; the PF6 anion is omitted for
clarity.
D a l t o n T r a n s . , 2 0 0 4 , 2 9 6 9 – 2 9 7 8
2 9 7 5

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Complex (anti-11) was treated with MCl2(cod) at room
temperature, generating yellow complexes formulated as anti-
[Cp*Ir(BDMPP-P,O)(dpmp-P1;P2,P3)MCl2](PF6)
(anti-14:
M = Pt; anti-15: M = Pd) by fluorescent X-ray analysis for anti-
1
14 and elemental analyses (Scheme 5). The H NMR spectra
showed a triplet around d 1.80 ppm due to the Cp* protons and
three singlets consisting of a 1:1:1 molar ratio in the range of
d 3.20–3.50 ppm due to the methoxy protons, suggesting the
magnetic inequivalence derived from the presence of the chiral
centers. The 31P{1H} NMR spectrum of anti-15 showed four
resonances at −5.85 (br), 14.7 (dd), 16.0 (dd) and 13.1 (d) ppm
for three P atoms of the dpmp ligand and the P1 nucleus of the
BDMPP-P,O ligand. Based on the spectroscopic data, anti-14
and anti-15 are assumed to have a structure with palladium or
platinum atom coordinated to two free P2 and P3 atoms at the
cis-positions.
Scheme 5 Reactions of anti-11, where P^P^P = (Ph2PCH2)2PPh,
L = 2,6-Me2C6H3 and R = C6H3-2,6-(MeO)2; the PF6 anions are omitted
for clarity.
Reaction of anti-11 with [Pd(XylNC)4](PF6)2 occurred readily,
giving a yellow complex (anti-16) in high yield, formulated as
[{Cp*Ir(BDMPP-P,O)(dpmp)}2{Pd(XylNC)2}](PF6)4. The IR
spectrum showed a sharp characteristic band at 2189 cm−1 due
to the terminal isocyanide, suggesting an anti-structure.
Fig. 5 Molecularstructureof [Cp*Ir(BDMPP-P,O){P(p-tolyl)3}](PF6)
(a) anti-13b and (b) syn-13b; the PF6 anion and hydrogen atoms are
omitted for clarity.
Molecular structures
Crystal structures of anti-2 and syn-2. Perspective drawings
of anti-2 and syn-2 with the atomic numbering schemes are
given in Fig. 1, and selected bond lengths and angles are listed
in Tables 2 and 3. anti-2 contains one molecule of water and
syn-2 contains = one molecule of CH2Cl2 and one of water, in
which the CH2Cl2 molecule is disordered. The Cp*IrCl moiety in
each complex is surrounded by the terminal and central P atoms
of the dpmp ligand, and the Cp*IrCl2 moiety coordinates to
another terminal P3 atom. The molecules have two chiral centers
at the Ir and central P2 atoms. Based on the priority order of the
ligands,6 the molecule with a RIrRP2/SP2SIr pair is the anti-form
and the other diastereomer with a RIrSP2 /RP2SIr pair is the syn-
form. The stereochemical difference is that the Cl atom and the
P-substituted Ph group occupy opposite sides in the anti-form
and the same side in the syn-form. The lengths (Ir–P and Ir–Cl)
and angles (P–Ir–P, P–Ir–Cl and Cl–Ir–Cl) around the iridium
atoms in both diastereomers are closely similar. The latter
angles are comparable with those found in the Rh or ruthenium
complexes bearing a similar anti-structure.4,5
found to be of great advantage in attacking to the metal atom
from the same side that the phenyl group exists. The preferential
formation of the anti-conformer is mainly responsible as a result
of the steric requirements in the transition state. Furthermore,
since the intermediate (IR) is more stable than the other (IS) and
the electron charge on the Rh metal of IS was calculated to be
poorer than that of IR (R-form), a facile nucleophilic attack of
Lewis bases to the intermediate (IS) should occur in comparison
with that to IR. Thus the anti-complexes (anti-11 and anti-13)
with an SIrSP0 pair would be preferentially formed rather than
anti-complexes with an RIrRS pair.
Crystal structure of anti-4. A perspective drawing of anti-
4 with the atomic numbering scheme is given in Fig. 2, and
selected bond lengths and angles are listed in Table 4. The mole-
cule has two half PF6 moieties with the P atoms on the inversion
center, and one of them shows disorder for the F atoms. Two
F atoms of one PF3 moiety are disordered. The framework bond
lengths and angles are fundamentally similar to those found in
anti-2. A characteristic feature was found in the P2chelate-C–P3free
bond angle of 111°, being narrower than the average P2
-
chelate
Fig. 6 Agostic Rh–H interaction in the intermediate (IR), (R)-
[{Cp*Rh(BDMPP-P,O)}+]‡ (from PM3 calculation): R = 2,6-
(MeO)2C6H3.
C–P3coordinate angle of 127° for 2. A similar trend was observed in
anti-11 having a free P3 atom (vide infra).
2 9 7 6
D a l t o n T r a n s . , 2 0 0 4 , 2 9 6 9 – 2 9 7 8

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Table 2 Selected bond lengths (Å) and angles (°) for anti-[Cp*IrCl(dpmp-P1,P2;P3)IrCl2Cp*](PF6)·H2O anti-2·H2O
Ir(1)–Cl(1)
Ir(2)–Cl(2)
P(1)–C(23)
P(3)–C(30)
2.386(2)
2.432(2)
1.843(5)
1.84(1)
Ir(1)–P(1)
Ir(2)–Cl(3)
P(2)–C(23)
2.299(2)
2.406(2)
1.840(6)
Ir(1)–P(2)
Ir(2)–P(3)
P(2)–C(30)
2.319(1)
2.309(1)
1.826(5)
Cl(1)–Ir(1)–P(1)
Ir(1)–P(1)–C(23)
Cl(2)–Ir(2)–P(3)
P(2)–C(30)–P(3)
85.64(5)
96.0(2)
89.55(5)
125.2(3)
Cl(1)–Ir(1)–P(2)
P(1)–C(23)–P(2)
Cl(3)–Ir(2)–P(3)
Ir(1)–P(2)–C(30)
87.71(5)
95.5(6)
88.91(5)
114.2(2)
P(1)–Ir(1)–P(2)
Cl(2)–Ir(2)–Cl(3)
Ir(2)–P(3)–C(30)
72.26(5)
88.95(6)
109.8(2)
Table 3 Selected bond lengths (Å) and angles (°) for syn-[Cp*IrCl(dpmp-P1,P2;P3)IrCl2Cp*](PF6)·CH2Cl2·H2O syn-2·CH2Cl2·H2O
Ir(1)–Cl(1)
Ir(2)–Cl(2)
P(1)–C(23)
P(3)–C(30)
2.369(4)
2.434(5)
1.79(2)
1.83(2)
Ir(1)–P(2)
Ir(2)–Cl(3)
P(2)–C(23)
2.313(4)
2.410(5)
1.82(2)
Ir(1)–P(1)
Ir(2)–P(3)
P(2)–C(30)
2.296(4)
2.311(4)
1.86(2)
Cl(1)–Ir(1)–P(1)
Ir(1)–P(1)–C(23)
Cl(2)–Ir(2)–P(3)
P(2)–C(30)–P(3)
87.4(2)
109.9(8)
88.6(2)
Cl(1)–Ir(1)–P(2)
P(1)–C(23)–P(2)
Cl(3)–Ir(2)–P(3)
Ir(2)–P(3)–C(30)
86.2(1)
96.3(8)
89.6(2)
107.5(5)
P(1)–Ir(1)–P(2)
Cl(2)–Ir(2)–Cl(3)
Ir(2)–P(3)–C(30)
71.6(1)
89.2(2)
107.5(5)
129.9(9)
Table 4 Selected bond lengths (Å) and angles (°) for anti-[Cp*IrCl(dpmp-P1,P2)](PF6)·CH2Cl2 anti-4·CH2Cl2
Ir(1)–Cl(1)
P(1)–C(13)
P(3)–C(20)
2.391(2)
1.853(7)
1.867(7)
Ir(1)–P(1)
P(2)–C(13)
2.292(2)
1.832(7)
Ir(1)–P(2)
P(2)–C(20)
2.304(2)
1.829(7)
Cl(1)–Ir(1)–P(1)
Ir(1)–P(1)–C(13)
Ir(1)–P(2)–C(20)
86.64(6)
95.9(2)
119.6(2)
Cl(1)–Ir(1)–P(2)
P(1)–C(13)–P(2)
P(2)–C(20)–P(3)
86.55(5)
94.2(3)
111.2(3)
P(1)–Ir(1)–P(2)
Ir(1)–P(2)–C(13)
72.01(6)
96.1(2)
Table 5 Selected bond lengths (Å) and (°) angles for [{Cp*IrCl(dpmp-P1,P2;P3)AuCl}2](PF6)2 8
Ir(1)–Cl
2.386(2)
2.295(2)
1.842(9)
1.827(7)
Ir(1)–P(1)
Au(1)–P(3)
P(2)–C(23)
2.294(2)
2.238(2)
1.839(8)
Ir(1)–P(2)
Au(1)–Au(1)*
P(2)–C(30)
2.324(2)
3.2114(6)
1.834(8)
Au(2)–Cl(2)
P(1)–C(23)
P(3)–C(30)
Cl(1)–Ir(1)–P(1)
Ir(1)–P(1)–C(23)
Cl(2)–Au(1)–P(3)
Au(1)*–Au(1)–P(3)
85.43(7)
95.5(3)
169.36(8)
105.26(5)
Cl(1)–Ir(1)–P(2)
P(1)–C(23)–P(2)
P(2)–C(30)–P(3)
85.61(7)
94.6(4)
120.4(4)
P(1)–Ir(1)–P(2)
Ir(1)–P(2)–C(23)
Au(1)*–Au(1)–Cl(2)
71.68(7)
94.6(3)
85.36(6)
Crystal structure of anti-8. A perspective drawing of anti-
8 with the atomic numbering scheme is given in Fig. 3, and
selected bond lengths and angles are listed in Table 5. The
molecule consists of a dimeric structure with a two-fold axis
in the middle of the Au–Au vector. The P(3)–Au(1)–Cl(2)
angle of 169.36(8)° bends somewhat from the linear array.
Two Au atoms, however, have apparently T-shape struc-
tures. The Au–Au bond length of 3.2114(6) Å is comparable
with that (3.203(2) Å) for the tetranuclear rhodium complex
[{Cp*RhCl2(dpmp-P1;P2;P3)Au}2](PF6)2 and is shorter than
the Au–Au lengths of 3.397(1) Å in a similar T-shape complex
[Au(SCN)(CNR)]2 (R = mesityl).21 The Au–Cl and Au–P(3)
lengths are 2.295(2) and 2.238(2) Å, respectively, compared
with those (2.297(2) and 2.245(2) Å)5 found in a similar type
of ruthenium mononuclear complex [(C6Me6)RuCl(dpmp-
P1,P2;P3)AuCl](PF6), whereas the Au–P(3) length is somewhat
shorter than the average Au–P bond length of 2.317(4) Å for the
tetranuclear complex [{Cp*RhCl2(dpmp-P1;P2;P3)Au}2](PF6)2
that is sterically crowded.4
group and dpmp ligand occupy opposite sides and the molecule
is assigned to the anti-form. The average Ir–P0 and Ir–O bond
lengths in the chelate ring are 2.319 and 2.094 Å, respectively,
compared with those found for the complexes bearing the P,O-
chelating structure.12,13 The average P0–Ir–O bite angle of 81.5°
is also in the usual range.
Crystal structures of anti- and syn-13b. Perspective drawings
of anti-13b and syn-13b with the atomic numbering schemes are
given in Fig. 5, and selected bond lengths and angles are listed
in Tables 7 and 8. The bond lengths and angles around the Ir
metal do not depend on the structures of the conformers. The
bond lengths around the Ir atom are not significantly different
from the starting complex syn-10.12 The average P(1)–Ir(1)–O(1)
bite angle of 81.7° is comparable with that (82.2°) of syn-10 and
anti-11. The average P(1)–Ir(1)–P(2) angles of 98.1° are wider
than the average P(2)–Ir(1)–O(1) angles of 85°. A similar trend
has been observed for anti-11. The P–Ir–Cl and Cl–Ir–O angles
in syn-10 are 86°. This is due to a difference of bulkiness between
tris-p-tolylphosphine and a Cl atom.
Crystal structure of anti-11. The complex consists of two
independent molecules (molecules 1 and 2) and contains a
CH2Cl2 molecule as a solvent molecule. A perspective draw-
ing of one independent molecule of anti-11 with the atomic
numbering scheme is given in Fig. 4, and selected bond lengths
and angles are listed in Table 6. The cyclopentadienyl group for
each molecule, one phenyl group for molecule 1 and two phenyl
groups for molecule 2 are disordered. One Cl atom of CH2Cl2
as a solvent molecule has an occupancy of 1.0 and the other
Cl atom has an occupancy of 0.5. The 2,6-dimethoxyphenyl
Summary
Reactions of dpmp with 1 at various molar ratios gave only the
binuclear complexes (anti- and syn-2), whereas reactions with
[Cp*RhCl2]2 or [(C6Me6)RuCl2]2 afforded mono- or binuclear
complexes, depending on the reaction conditions. Mononuclear
complex (4) was treated with AuCl(SC4H8), generating the
binuclear complex (8), [{Cp*Ir(dpmp-P1,P2;P3)AuCl}2](PF6)2.
The reaction with the ruthenium analog gave a monomeric
D a l t o n T r a n s . , 2 0 0 4 , 2 9 6 9 – 2 9 7 8
2 9 7 7

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Table 6 Selected bond lengths (Å) and angles (°) for [{Cp*Ir(BDMPP-P,O)(dpmp-P1)}(PF6)2·CH2Cl2 anti-11·CH2Cl2
Ir(1)–P(1)
Ir(2)–P(5)
P(1)–C(21)
P(5)–C(98)
P(2)–C(58)
P(4)–C(65)
P(7)–C(147)
2.316(2)
2.323(2)
1.803(10)
1.810(9)
1.832(9)
1.853(10)
1.84(1)
Ir(1)–P(2)
Ir(2)–P(6)
O(1)–C(26)
O(5)–C(103)
P(3)–C(58)
P(6)–C(140)
P(8)–C(147)
2.349(2)
2.345(2)
1.35(1)
1.332(10)
1.860(8)
1.819(9)
1.851(9)
Ir(1)–O(1)
Ir(2)–O(5)
C(21)–C(26)
C(98)–C(103)
P(3)–C(65)
P(7)–C(140)
2.089(6)
2.099(5)
1.41(1)
1.39(1)
1.84(1)
1.880(8)
P(1)–Ir(1)–P(2)
P(5)–Ir(2)–P(6)
95.42(8)
95.67(8)
101.8(3)
121.2(8)
119.8(5)
121.9(5)
114.6(3)
111.6(5)
P(1)–Ir(1)–O(1)
P(5)–Ir(2)–O(5)
P(1)–C(21)–C(26)
Ir(2)–P(5)–C(98)
O(5)–C(103)–C(98)
C(58)–P(3)–C(65)
P(6)–C(140)–P(7)
81.4(2)
81.5(2)
113.9(7)
101.3(3)
123.4(8)
98.1(4)
P(2)–Ir(1)–O(1)
P(6)–Ir(2)–O(5)
Ir(1)–O(1)–C(26)
P(5)–C(98)–C(103)
Ir(1)–P(2)–C(58)
P(3)–C(65)–P(4)
C(140)–P(7)–C(147)
83.3(2)
82.4(2)
120.8(5)
113.4(7)
114.9(3)
112.1(5)
99.1(4)
Ir(1)–P(1)–C(21)
O(1)–C(26)–C(21)
Ir(2)–O(5)–C(103)
P(2)–C(58)–P(3)
Ir(2)–P(6)–C(140)
P(7)–C(147)–P(8)
120.9(5)
Table 7 Selected bond lengths (Å) and angles (°) for anti-[Cp*Ir(BDMPP-P,O){P(p-tolyl)3}](PF6) anti-13b
Ir(1)–P(1)
2.315(2)
98.84(8)
Ir(1)–P(2)
2.37(1)
81.3(1)
Ir(1)–O(1)
2.104(5)
P(1)–Ir(1)–P(2)
P(1)–Ir(1)–O(1)
P(2)–Ir(1)–O(1)
83.1(2)
Table 8 Selected bond lengths (Å) and angles (°) for anti-[Cp*Ir(BDMPP-P,O){P(p-tolyl)3}](PF6) syn-13b
Ir(1)–P(1)
2.332(2)
97.40(7)
Ir(1)–P(2)
2.335(2)
82.0(1)
Ir(1)–O(1)
2.089(4)
86.8(2)
P(1)–Ir(1)–P(2)
P(1)–Ir(1)–O(1)
P(2)–Ir(1)–O(1)
complex [(C6Me6)Ru(dpmp-P1,P2;P3)AuCl](PF6) and in the
rhodium analog, the tetranuclear complex [{Cp*RhCl2(dpmp-
P1,P2,P3)Au}2](PF6)2 was formed. The three starting complexes
are isoelectronic complexes with d6 configuration, but their
reactivity was found to be different. These iridium complexes
as well as the rhodium and ruthenium analogs are expected to
be potential precursors for leading to formation of polynuclear
complexes.
The demethylation derived from the reactions between
[Cp*MCl2]2 (M = Ir, Rh) and BDMPP led to the formation of
thermodynamically stable products, syn-10 or syn-12. Substitu-
tion reactions of syn-10 with Lewis bases in the presence of KPF6
proceeded preferentially with inversion. The demethylation
reaction proceeded with thermodynamic control and the sub-
stitution reaction proceeded with kinetic control. Based on the
PM3 calculation, a factor to control the latter reaction that
was assumed to be responsible was the steric requirement of
a coordinatively unsaturated intermediate [Cp*M(BDMPP-
P,O)+]‡ (M = Ir, Rh).
2 (a) T. Tanase and Y. Yamamoto, Trends Organomet. Chem., 1999,
35, and references cited therein; (b) T. Tanase, Bull. Chem. Soc. Jpn.,
2002, 75, 1407.
3 Y. Kosaka, Y. Shinozaki, Y. Tsutsumi, Y. Kaburagi, Y. Yamamoto,
Y. Sunada and K. Tatsumi, J. Organomet. Chem., 2003, 671, 8.
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K. Tatsumi, Eur. J. Inorg. Chem., 2004, 134.
5 Y. Yamamoto, Y. Sinozaki, Y. Tsutsumi, K. Fuse, K. Kuge,
Y. Sunada and K. Tatsumi, Inorg. Chim. Acta, 2004, 357, 1270.
6 See refs. 3 and 4 on the naming of syn- and anti-forms.
7 J. W. Kang, K. Moseley and P. M. Maitlis, J. Organomet. Chem.,
1975, 87, 359.
8 H. M. Walborsky and G. E. Niznik, J. Org. Chem., 1972, 37, 187.
9 R. Appel, K. Geisler and H. F. Schöler, Chem. Ber., 1979, 112,
648.
10 R. Uson, A. Laguna and M. Laguna, Inorg. Synth., 1989, 26, 86.
11 (a) Y. Yamamoto and H. Yamazaki, Bull. Chem. Soc., Jpn., 1985,
58, 1843; (b) Y. Yamamoto, K. Takahashi and H. Yamazaki, Bull.
Chem. Soc., Jpn., 1987, 60, 1843.
12 Y. Yamamoto, K. Kawasaki and S. Nishimura, J. Organomet. Chem.,
1999, 587, 49.
13 D. T. Cromer and J. T. Waber, International Tables for X-ray Crystal-
lography, Kynoch Press, Birmingham, UK, 1974, Table 2.2A.
14 J. A. Ibers and W. C. Hamilton, Acta Crystallogr., 1964, 17, 718.
15 D. C. Creagh and W. J. McAulley, International Tables for Crystallo-
graphy, Vol. C, Kluwer, Boston, 1992, Table 4.2.6.8, pp. 219–222.
16 TEXSAN: Crystal Structure Analysis Package, Molecular Structure
Corporation, Houston, TX, 1985 and 1992.
17 SHELXL-97: G. M. Sheldrick, Program for the refinement of
Crystal Structures. University of Göttingen, Germany, 1997.
18 Y. Yamamoto, X.-H. Han and K. Sugawara, J. Chem. Soc., Dalton
Trans., 2002, 195.
Acknowledgements
The authors would like to thank Professor Akira Nakamura
for helpful suggestions. This work was partially supported by
a Grant-in Aid for Scientific Research from Ministry of Educa-
tion, Science, Culture and Sports, Japan. We are also grateful to
the Materials Analysis Center, ISIR, Osaka University, for their
support with X-ray diffraction studies and elemental analyses.
19 The calculations were performed by using the Rh complexes because
the parameters for Ir atom are not available.
20 Although X-ray analyses of the main product (anti-13a) for 13a and
the minor product (syn-13c) for 13c were carried out, the quality of
the structure determinations were poor. The gross structural details,
however, are not in doubt.
References and notes
1 (a) A. L. Balch, Prog. Inorg. Chem., 1994, 41, 239, and references
cited therein; (b) A. L. Balch, Pure Appl. Chem., 1988, 60, 555;
(c) A. L. Balch, L. A. Fossett, J. Linehan and M. M. Olmstead,
Organometallics, 1990, 5, 1638; (d) A. L. Balch, V. J. Catalano and
M. M. Olmstead, J. Am. Chem. Soc., 1990, 112, 2010.
21 T. Mathieson, A. Schier and H. Schmidbauer, J. Chem. Soc., Dalton
Trans., 2001, 1196.
2 9 7 8
D a l t o n T r a n s . , 2 0 0 4 , 2 9 6 9 – 2 9 7 8