Preparation and characterization of pentamethylcyclopentadienylrhodium(III) and iridium(III), and (arene)ruthenium(II) complexes of 1,8- bis(diphenylphosphinomethyl)naphthalene

Article abstract of DOI:10.1016/S0020-1693(02)00797-1

1,8-Bis(diphenylphosphinomethyl)naphthalene (1,8-dpmn) reacted with [(arene)RuCl₂]₂ (1) or [Cp*MCl₂] ₂ (2: M=Rh; 3: M=Ir) to generate the corresponding diphosphine-bridged complexes, [{(arene)RuCl₂}₂(1,8-dpmp- P,P′)] (4) (arene=p-cymene (a), 1,2,3-Me₃C₆H ₃ (b), 1,2,3,4-Me₄C₆H₂ (d), 1,2,3,5-Me₄C₆H₂ (d), C₆Me ₆ (e)) or [(Cp*MCl₂)₂(1,8-dpmp-P, P′)] (5: M=Rh; 6: M=Ir). Homonuclear complexes [{(p-cymene)RuCl ₂}(1,8-dpmp-P,P′){(arene)RuCl₂}] 7ab and 7ad bearing different arene groups were prepared by the reactions of 1a with 1b (or 1d). They existed as two isomers in solution. Reactions of 2 with 1 or 3 gave heteronuclear complexes [(Cp*RhCl₂)(1,8-dpmp-P,P′) {(arene)RuCl₂}] (8) and [(Cp*RhCl₂)(1,8-dpmp-P, P′)(Cp*IrCl₂)] (10). The heteronuclear complexes of iridium-ruthenium 9 were generated from 1 to 2. Complexes 1, 2 and 3 reacted with 1,8-dpmp in the presence of AgOTf to give the cationic complexes, [(arene)RuCl(1,8-dpmp-P,P′)](OTf) (11) or [Cp*MCl(1,8-dpmp-P, P′)](OTf) (12: M=Rh; 13: M=Ir) that showed the presence of isomers in solution. They were treated with Ag(OTf) to afford the Cl-bridged complexes, [{(p-cymene)Ru(μ-Cl)}₂(1,8-dpmp-P,P′)](OTf)₂ (15a) or [{Cp*M(μ-Cl)}₂(1,8-dpmp-P,P′)](OTf) ₂ (16: M=Rh; 17: M=Ir). Complexes 16 and 17 cleaved the Cl-bridges with xylyl or mesityl isocyanide to generate the dimeric isocyanide complexes [{Cp*MCl(RNC)}₂(1,8-dpmp-P,P′)](OTf)₂ (18: M=Rh; 19: M=Ir). X-ray analyses of 5, 8b, 10, 11a, 12, 15a and 18b were performed.

Full text of DOI:10.1016/S0020-1693(02)00797-1

Inorganica Chimica Acta 334 (2002) 77ꢁ90
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www.elsevier.com/locate/ica
Preparation and characterization of
pentamethylcyclopentadienylrhodium(III) and iridium(III), and
(arene)ruthenium(II) complexes of 1,8-
bis(diphenylphosphinomethyl)naphthalene
Yasuhiro Yamamoto *, Fumio Miyauchi
Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan
Received 12 September 2001; accepted 25 January 2002
Abstract
1,8-Bis(diphenylphosphinomethyl)naphthalene (1,8-dpmn) reacted with [(arene)RuCl2]2 (1) or [Cp*MCl2]2 (2: Mꢀ
to generate the corresponding diphosphine-bridged complexes, [{(arene)RuCl2}2(1,8-dpmp-P,P?)] (4) (areneꢀp-cymene (a), 1,2,3-
Me3C6H3 (b), 1,2,3,4-Me4C6H2 (d), 1,2,3,5-Me4C6H2 (d), C6Me6 (e)) or [(Cp*MCl2)2(1,8-dpmp-P,P?)] (5: MꢀRh; 6: MꢀIr).
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Rh; 3: MꢀIr)
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/
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Homonuclear complexes [{(p-cymene)RuCl2}(1,8-dpmp-P,P?){(arene)RuCl2}] 7ab and 7ad bearing different arene groups were
prepared by the reactions of 1a with 1b (or 1d). They existed as two isomers in solution. Reactions of 2 with 1 or 3 gave
heteronuclear complexes [(Cp*RhCl2)(1,8-dpmp-P,P?) {(arene)RuCl2}] (8) and [(Cp*RhCl2)(1,8-dpmp-P,P?)(Cp*IrCl2)] (10). The
heteronuclear complexes of iridiumꢁ
presence of AgOTf to give the cationic complexes, [(arene)RuCl(1,8-dpmp-P,P?)](OTf) (11) or [Cp*MCl(1,8-dpmp-P,P?)](OTf) (12:
MꢀRh; 13: MꢀIr) that showed the presence of isomers in solution. They were treated with Ag(OTf) to afford the Cl-bridged
complexes, [{(p-cymene)Ru(m-Cl)}2(1,8-dpmp-P,P?)](OTf)2 (15a) or [{Cp*M(m-Cl)}2(1,8-dpmp-P,P?)](OTf)2 (16: MꢀRh; 17:
MꢀIr). Complexes 16 and 17 cleaved the Cl-bridges with xylyl or mesityl isocyanide to generate the dimeric isocyanide complexes
[{Cp*MCl(RNC)}2(1,8-dpmp-P,P?)](OTf)2 (18: MꢀRh; 19: MꢀIr). X-ray analyses of 5, 8b, 10, 11a, 12, 15a and 18b were
performed. # 2002 Elsevier Science B.V. All rights reserved.
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ruthenium 9 were generated from 1 to 2. Complexes 1, 2 and 3 reacted with 1,8-dpmp in the
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Keywords: Rh and Ir complexes; 1,8-Bis(diphenylphosphinomethyl)naphthalene; Pentamethylcyclopentadienyl group
1. Introduction
[1d,1f,2]. They are assumed to have potential signifi-
cance in metal-assisted reactions, since they are mem-
bers of a class of bidentate ligands with a rigid C3-
1,8-Diorganophosphino-substituted
naphthalenes
and their derivative are interested in the structures and
properties. Recently, the chemistry has been developed
by Schmutzler et al. [1]. Since 1,8-bis(diphenylpho-
sphino)naphthalene (1,8-dppn) and 1,8-bis(dimethyl-
phosphino)naphthalene have the Pꢀ ꢀ ꢀP distance of
backbone
[4].
1,8-Bis(diphenylphosphinomethyl)-
naphthalene (1,8-dpmn) generated from the introduc-
tion of a methylene group between the naphthalene ring
and phosphorus atom is less rigid than 1,8-dppn and its
derivatives, and has the potential of various coordina-
tion modes except chelation. It is assumed to be the
potential ligand of catalytic reactions by transition-
metal complexes. There are few examples of metal
complexes bearing 1,8-dpmn ligand. Recently, Tin et
al. reported the preparation of RuH2(CO)(PPh3)(1,8-
dpmn) with a chelate structure [5]. We reported that the
˚
˚
3.052 and 3.070 A (and 3.036 A), respectively, well
˚
within the sum of the van der Waals radii (3.80 A)
[1a,2,3], they are very rigid in its manner of coordination
because of the direct binding of the phosphorus atom to
the naphthalene ring, and forms chelated complexes
reactions of [M2(CNR)6](PF6)2 (MꢀPd, Pt) with 1,8-
/
dpmn generated dinuclear palladium and platinum
complexes, [M2(RNC)4(1,8-dpmn-P,P?)](PF6)2 and
* Corresponding author. Fax: ꢂ
E-mail address: yamamoto@chem.sci.toho-u.ac.jp (Y. Yamamoto).
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81-47-475 1855.
0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 0 - 1 6 9 3 ( 0 2 ) 0 0 7 9 7 - 1

78
Y. Yamamoto, F. Miyauchi / Inorganica Chimica Acta 334 (2002) 77ꢁ90
/
[M2(RNC)2(1,8-dpmn-P,P?)2](PF6)2 (Mꢀ
/
Pd, Pt) [6].
PCH2, 4H), 6.6ꢁ
d 35.9(s). Calc. for C56H58P2Cl4Ru2×
/
7.4 (m, ArH). 31P{1H} NMR (CDCl3):
0.5CH2Cl2: C,
These complexes have chelated structures. We report
here the reactions of 1,8-dpmn with bis[dichloro(penta-
methylcyclopentadienyl)rhodium(III) (or iridium(III))]
or bis[dichloro(arene)ruthenium(II)] to form complexes
bearing chelation and m-coordination of 1,8-dpmn
ligand.
/
57.54; H, 5.04. Found: C, 57.77; H, 5.09%.
[(1,2,3,5-Me4C6H2)RuCl2}(m-1,8-dpmn)] (4d) (orange,
43.7%): UVꢁVis (CH2Cl2): lmax 372, approximately
/
1
310(sh) nm. H NMR (CDCl3): d 1.48 (s, 5-Me, 6H),
1.87 (s, 1- and 3-Me, 12H), 1.96 (s, 2-Me, 6H), 4.34 (s, 4-
and 6-C6H, 4H), 4.50 (d, JPH
5.29 (s, CH2Cl2), 6.4ꢁ
7.4 (m, ArH). 31P{1H} NMR
(CDCl3): d 34.6(s). Calc. for C56H58P2Cl4Ru2×CH2Cl2:
C, 56.03 H, 4.95. Found: C, 55.38; H, 5.01%.
[{(C6Me6)RuCl2}2(m-1,8-dpmn)] (4e) (reddish brown,
ꢀ
/
10.0 Hz, PCH2, 4H),
/
2. Experimental
/
All reactions were carried out under nitrogen atmo-
sphere. 1,8-dpmn [6], isocyanides [7], [Cp*MCl2]2 [8,9]
1
44.3%): UVꢁ
NMR (CDCl3): d 1.67 (s, Me, 32H), 4.14 (d, JPH
Hz, PCH2, 4H), 5.29 (s, CH2Cl2), 6.4ꢁ7.4 (m, ArH).
31P{1H} NMR (CDCl3):
35.1(s). Calc. for
C60H66P2Cl4Ru2×0.25CH2Cl2: C, 59.59; H, 5.52. Found:
C, 59.48; H, 5.73%.
/
Vis (CH2Cl2): lmax 374, 310 (sh) nm. H
(1: Mꢀ
/
Rh, 2: Ir; Cp*ꢀ
/
C5Me5) and [(arene)RuCl2]2 (3)
ꢀ/8.0
[10] (a: p-cymene; b: 1,2,3-Me3C6H3; c: 1,2,3,4-
Me4C6H2; d: 1,2,3,4-Me4C6H2; e: C6Me6) were prepared
according to the literature. Dichloromethane was dis-
tilled over CaH2 and diethyl ether was distilled over
LiAlH4. The IR spectra measured on an FT/IR-5300.
NMR spectroscopy was carried out on Bruker AC250.
/
d
/
[(Cp*RhCl2)2(m-1,8-dpmn)] (5) (orange, 84.3%): UVꢁ
/
1
Vis (CH2Cl2): lmax 415 nm. H NMR (CDCl3): d 1.27
1
The H NMR spectra were measured at 250 MHz and
31P{1H} NMR spectra were measured at 101 MHz using
85% H3PO4 as an external reference.
(d, JPH
7.2 (m, ArH). 31P{1H} NMR (CDCl3): d 37.9 (d,
JRhP 2CH2Cl2:
141 Hz). Calc. for C56H60P2Cl4Rh2×
C, 53.08 H, 4.91. Found: C, 53.36; H, 5.14%.
[(Cp*IrCl2)2(m-1,8-dpmn)] (6) (orange, 84.6%): UVꢁ
ꢀ
/
3.5 Hz, Cp*, 30H), 4.63 (b, PCH2, 4H), 6.9ꢁ
/
ꢀ
/
/
2.1. Preparation of dinuclear complexes
/
1
Vis (CH2Cl2): lmax 319 nm. H NMR (CDCl3): d 1.28
(d, JPH 2.5 Hz, Cp*, 30H), 4.68 (b, PCH2, 4H), 6.4ꢁ
7.6 (m, ArH). 31P{1H} NMR (CDCl3): d 5.3 (s). Calc.
for C56H60P2Cl4Ir2×CH2Cl2: C, 48.69 H, 4.44. Found: C,
48.52; H, 4.53%.
2.1.1. [{(p-Cymene)RuCl2}2(m-1,8-dpmn)] (4a)
ꢀ
/
/
A mixture of [(p-cymene)RuCl2]2 (160.7 mg, 0.262
mmol) and 1,8-dpmn (145.5 mg, 0.277 mmol) was
stirred in CH2Cl2 (15 ml) at room temperature (r.t.)
for 24 h. The solution was concentrated and diethylether
was added, giving reddish brown crystals of 4a (253.2
/
mg, 84.7%). UVꢁ
1H NMR (CDCl3): d 1.01 (d, JHH
12H), 1.75 (s, Me, 6H), 2.52 (sep. JHH
2H), 4.77 (d, 2JPH
9.5 Hz, PCH2, 4H), 5.17 (d, JHH
6.0 Hz, 2,6- or 3,5-C6H, 4H), 5.33 (d, JHH 6.0 Hz, 2,6-
or 3,5-C6H, 4H), 5.30 (s, CH2Cl2), 6.56ꢁ7.43 (m, ArH).
31P{1H} NMR(CDCl3):
31.4 (s). Calc. for
C56H58P2Cl4Ru2×1.5CH2Cl2: C, 54.62; H, 4.86. Found:
/
Vis (CH2Cl2): lmax 371, 310(sh) nm.
7.0 Hz, Me2C,
7.0 Hz, CH,
2.1.2. [{(p-Cymene)RuCl2}{(1,2,3-
ꢀ
/
Me3C6H3)RuCl2}(m-1,8-dpmn)] (7ab) (brown, 37.9%)
To a mixture of [(p-cymene) RuCl2]2 (1a) (31.0 mg,
0.051 mmol) and [(1,2,3-Me3C6H3)RuCl2]2 (1b) (33.5
mg, 0.057 mmol) in CH2Cl2 (20 ml) and acetone (20 ml)
was added 1,8-dpmp (58.5 mg, 0.112 mmol) at r.t. and
stirred over night. After the solution was concentrated
to approximately 3 ml, diethylether was added to give
ꢀ
/
ꢀ
/
ꢀ
/
ꢀ
/
/
d
/
C, 54.95; H, 4.92%. The following complexes were
prepared according to a procedure similar to 4a.
[{(1,2,3-Me3C6H3)RuCl2}2(m-1,8-dpmn)] (4b) (reddish
brown crystals of 7ab (43.1 mg, 37.9%). UVꢁ
/
Vis
(CH2Cl2): lmax 371, 300(sh) nm. H NMR (CDCl3): d
0.96 (d, JHH 5.5 Hz, i-
5.5 Hz, i-Pr)*a, 0.99 (d, JHH
Pr)*b, 1.74 (s, p-Me, 3H), 1.93 (s, 1- and 3-Me, 6H), 2.08
(d, JPH
2.5 Hz, 2-Me, 3H), 2.49 (c, CH, 1H)*a,b, 4.30
(d, JHH 5.0 Hz,
5.0 Hz, 5-C6H, 1H)*a, 4.34 (d, JHH
5-C6H, 1H)*b, ca. 4.73 (c, 4- and 6-C6H, and PCH2,
4H), 5.09 (d, JHH
6.5 Hz, 2,6- or 3,5-C6H, 2H)*a, 5.12
(d, JHH
6.5 Hz, 2,6- or 3,5-C6H, 4H)*b, 5.27 (d,
JHH 6.5
6.5 Hz, 2,6- or 3,5-C6H, 2H)*a, 5.31 (d, JHH
7.43 (m, ArH, 26H).
1
ꢀ
/
ꢀ
/
brown, 60.0%): UVꢁ
nm. 1H NMR (CDCl3): d 1.94 (s, 1,3-Me, 12H), 2.11 (d,
JPH 2.5 Hz, 2-Me, 6H), 4.31 (d, JHH 3.0 Hz, 4,6-
C6H, 4H), 4.73 (d, JPH 9.0 Hz, PCH2, 4H), 5.29 (s,
CH2Cl2), 6.63 (t, JHH 3.0 Hz, 5-C6H, 2H), 6.5ꢁ7.4 (m,
ArH, 26H). 31P{1H} NMR (CDCl3): d 36.7 (s). Calc. for
C54H54P2Cl4Ru2×CH2Cl2: C, 55.33; H, 4.73. Found: C,
55.29; H, 4.73%.
[(1,2,3,4-Me4C6H2)RuCl2}2(m-1,8-dpmn)] (4c) (red-
dish brown, 39.4%): UVꢁVis (CH2Cl2): lmax 371,
310(sh) nm. H NMR (CDCl3): d 1.67 (s, 1,4- or 2,3-
Me, 12H), 2.10 (d, JPH 2.3Hz, 1,4- or 2,3-Me, 12H),
4.26 (d, JPH 3.0 Hz, 5,6-C6H), 4.71 (d, JPH
/
Vis (CH2Cl2): lmax 370, 300(sh)
ꢀ
/
ꢀ
/
ꢀ
/
ꢀ
/
ꢀ
/
2
ꢀ
/
ꢀ
/
/
ꢀ
/
ꢀ
/
/
ꢀ
/
ꢀ
/
Hz, 2,6- or 3,5-C6H, 4H)*b, 6.56ꢁ
/
31P{1H} NMR (CDCl3): d 31.5 (s, (p-cymene)RuP)*a,
32.2 (s, (p-cymene)RuP)*b, 36.2 (s, (1,2,3-Me3-
C6H3)RuP)*a, 38.8 (s, (1,2,3-Me3C6H3)RuP)*b. Isomer
/
1
ꢀ
/
ratio: A/Bꢀ
/
1.3. Calc. for C55H56P2Cl4Ru2: C, 58.83; H,
2
ꢀ
/
ꢀ9.5 Hz,
/
5.03. Found: C, 59.08; H, 5.01%.

Y. Yamamoto, F. Miyauchi / Inorganica Chimica Acta 334 (2002) 77ꢁ
/90
79
[{(p-Cymene)RuCl2}{(1,2,3,5-Me4C6H2)RuCl2}(m-
1,8-dpmn)] (7ad) (brown, 59.3%). UVꢁVis (CH2Cl2):
lmax 375, ca. 310(sh) nm. H NMR (CDCl3): d 0.95 (d,
JHH 7.0 Hz, i-Pr,
7.0 Hz, i-Pr, 6H)*a, 0.98 (d, JHH
ratio: A/Bꢀ
3.1. Calc. for C56H59P2Cl4RuRh.CH2Cl2:
C, 55.90 H, 5.02. Found: C, 55.52; H, 4.98%.
/
/
1
[{(p-Cymene)RuCl2}(m-1,8-dpmn)(Cp*IrCl2)]
(9a)
(orange, 58.5%). UVꢁVis (CH2Cl2): lmax 320 nm.
/
ꢀ
/
ꢀ
/
1
FAB mass (m/z): 1194 [(M-Cl)ꢂ]. H NMR (CDCl3):
d 0.96 (d, JHH 7.0
7.0 Hz, i-Pr, 6H)*a, 0.98 (d, JHH
Hz, i-Pr, 6H)*b, 1.29 (d, JPH
2.5 Hz, Cp*, 15H), 1.56
(s, p-Me, 3H), 2.51 (c, CH, 2H), 4.58 (d, JHH 9.0 Hz,
p-cymene, 2H)*a, 4.74 (d, JHH
9.0 Hz, p-cymene,
2H)*a, 5.01 (d, JPH 9.0 Hz, PCH2, 2H)*b, 5.14 (d,
JPH 5.0 Hz, p-
6.5 Hz, PCH2, 2H)*b, 5.31 (d, JHH
cymene, 2H)*a, 5.38 (d, JHH 5.5 Hz, p-cymene, 2H)*b,
6.45ꢁ
7.70 (m, ArH, 26H). 31P{1H} NMR (CDCl3): d
31.3, 31.5 (s, p-cymeneRu), 6.8 (s, Cp*IrP). Isomer
ratio: A/Bꢀ3.1. Calc. for C56H59P2Cl4RuIr: C, 54.72;
6H)*b, 1.49 (s, 5-Me, 3H)*a, 1.53 (s, 5-Me, 3H)*b, 1.73
(s, p-Me of p-cymene, 3H)*a, 1.74 (s, p-Me of p-cymene,
3H)*b, 1.86 (s, 1- and 3-Me, 6H)*a, 1.94 (s, 1- and 3-Me,
6H)*b, 2.50 (c, CH, 1H), 4.33 (s, 4- and 6-H, 2H), 4.55
ꢀ
/
ꢀ
/
ꢀ
/
ꢀ
/
10 Hz, PCH2, 2H)*a, 4.73 (d, JHH
6.0 Hz, PCH2, 2H)*b, 6.45ꢁ
ꢀ
/
5.0 Hz,
ꢀ
/
(d, JPH
C6H4, 2H)*a, 5.13 (d, JPH
7.40 (m, ArH, 26H). 31P{1H} NMR (CDCl3): d 31.2,
31.5 (s, (p-cymene)RuP), 35.8 (s, (1,2,3,5-
Me4C6H2)RuP). Isomer ratio: A/Bꢀ1.8. Calc. for
C56H58P2Cl4Ru2×
CH2Cl.2: C, 56.03; H, 4.95. Found: C,
56.44; H, 5.24%.
[{(p-Cymene)RuCl2}(m-1,8-dpmn)(Cp*RhCl2)] (8a)
(brown, 51.7%). UVꢁVis (CH2Cl2): lmax 395, ca.
340(sh) nm. FAB mass (m/z): 1105 [(M-Cl-1)ꢂ]. 1H
NMR (CDCl3): d 0.96 (d, JHH
7.0 Hz, i-Pr, 6H)*a,
0.98 (d, JHH 4.0 Hz,
7.0 Hz, i-Pr, 6H)*b, 1.29 (d, JPH
Cp*, 15H)*a,b, 1.73 (s, p-Me, 3H)*a, 1.74 (s, p-Me,
3H)*b, 2.50 (c, CH, 1H), 4.57 (d, JHH
9.0 Hz, p-
cymene, 2H)*a, 4.74 (d, JPH 9.0 Hz, PCH2, 2H)*a, 4.98
(d, JHH
9.0 Hz, p-cymene, 2H)*b, 5.14 (d, JPH
Hz, PCH2, 2H)*b, 5.29 (s, CH2Cl2), 5.32 (d, JHH
Hz, p-cymene, 2H)*a, 5.42 (d, JHH
2H)*b, 6.45ꢁ
(CDCl3): d 31.2, 31.5 (s, p-cymeneRu), 35.8 (d,
JRhP 142.0 Hz, RhP). Isomer ratio: A/Bꢀ1.8. Calc.
1.5CH2Cl2: C, 54.50; H, 4.93.
ꢀ
/
ꢀ
/
ꢀ
/
/
ꢀ
/
ꢀ
/
ꢀ
/
/
/
/
/
H, 4.84. Found: C, 54.48; H, 5.17%.
[{(1,2,3-Me3C6H3)RuCl2}(m-1,8-dpmn)(Cp*IrCl2)]
/
(9b) (orange, 66.8%). UVꢁVis (CH2Cl2): lmax approxi-
/
1
mately 360 (sh), 311 nm. H NMR (CD2Cl2): d 1.25 (d,
JPH 2.5 Hz, Cp*,
2.5 Hz, Cp*, 15H)*a, 1.26 (d, JPH
15H)*b, 1.90 (s, 1- and 3-Me, 6H)*a, 1.91 (s, 1- and 3-
Me, 6H)*b, 2.07 (d, JPH 2.5Hz, 2-Me, 3H)*a, 2.08 (d,
JPH 5.4 (m, 4-, 5-, 6-C6H,
2.5 Hz, 2-Me, 3H)*b, 4.25ꢁ
and PCH2), 5.29 (s, CH2Cl2), 6.5ꢁ7.4 (m, ArH, 26H).
31P{1H} NMR (CDCl3): d 5.7, 6.5 (s, Cp*IrP), 34.5,
35.5 (s, RuP). Isomer ratio: A/Bꢀ4.7. Calc. for
0.5CH2Cl2: C, 53.01; H, 4.65. Found:
ꢀ
/
ꢀ
/
ꢀ
/
ꢀ
/
ꢀ
/
ꢀ
/
ꢀ
/
ꢀ
/
/
ꢀ
/
/
ꢀ
/
ꢀ
/
4.5
5.0
ꢀ
/
/
ꢀ
/
5.0 Hz, p-cymene,
C55H57P2Cl4RuIr×
/
/
7.70 (m, ArH, 26H). 31P{1H} NMR
C, 52.76; H, 4.72%.
[(Cp*RhCl2)(m-1,8-dpmn)(Cp*IrCl2)] (10) (reddish
ꢀ
/
/
brown, 91.7%). UVꢁVis (CH2Cl2): lmax 394, ca.
/
for C56H59P2Cl4RuRh×
/
310(sh) nm. 1H NMR (CDCl3): d 1.26 (d, JPH
Hz, Cp*Ir, 15H), 1.27 (d, JPH 3.5 Hz, Cp*Rh, 15H),
4.65 (b, PCH2, 4H), 5.30 (s, CH2Cl2), 6.4ꢁ7.4 (m, ArH,
26H). 31P{1H} NMR (CDCl3): d 5.23 (s, Cp*IrP), 37.9
(d, JRhH
ꢀ2.5
/
Found: C, 54.67; H, 5.28%.
ꢀ
/
[{1,2,3-Me3C6H3RuCl2}(m-1,8-dpmn)(Cp*RhCl2)]
/
(8b) (yellow, 38.7%). UVꢁ
/
Vis (CH2Cl2): lmax 395, ca.
4.0
Hz, Cp*, 15H)*a,b, 1.91 (s, 1- and 3-Me, 6H)*a, 1.92 (s,
1- and 3-Me, 6H)*b, 2.06 (d, JPH 3.0 Hz, 2-Me, 3H)*a,
2.09 (d, JPH 5.0
3.0 Hz, 2-Me, 3H)*a, 4.29 (d, JHH
Hz, 4,6-Me, 6H)*a, 4.36 (d, JHH
5.0 Hz, 4- and 6-Me,
6H)*b, 4.60 (d, JPH
4.0 Hz, PCH2, 2H), 4.69 (d, JHH
4.0 Hz, PCH2, 2H), 5.92 (t, JHH 5.0 Hz, 5-C6H, 1H),
6.45ꢁ
7.50 (m, ArH, 26H). 31P{1H} NMR (CDCl3): d
36.7, 36.8 (s, (p-cymene)RuP), 39.3 (d, JRhP 143.0 Hz,
Cp*RhP). Isomer ratio: A/Bꢀ1.2. Calc. for
1
340(sh) nm. H NMR (CDCl3): d 1.28 (d, JRhH
ꢀ
/
ꢀ
/
142.0 Hz). Calc. for C56H60P2Cl4RhIr×
/
1.5CH2Cl2: C, 50.80 H, 4.67. Found: C, 50.92; H, 4.23%.
ꢀ
/
ꢀ
/
ꢀ
/
2.2. Preparation of cationic complexes
ꢀ
/
ꢀ
/
ꢀ
/
2.2.1. [{(p-Cymene)RuCl(1,8-dpmn)](OTf) (11a)
A solution of [(p-cymene)RuCl2]2 (72.2 mg, 0.118
mmol) in CH2Cl2 (15 ml) and acetone (5 ml) was stirred
at r.t. for 10 min. Ag(OTf) (70.2 mg, 0.273 mmol) was
added to the solution and then 1,8-dpmn (125.6 mg,
0.239 mmol) was added. After 5 h, the solvent was
removed and the residue was extracted with CH2Cl2,
followed by filtration through the glass filter (G4). The
CH2Cl2 was concentrated and diethylether was added,
ꢀ
/
/
ꢀ
/
/
C55H57P2Cl4RuRh: C, 58.68; H, 5.10. Found: C,
58.83; H, 5.16%.
[(1,2,3,4-Me4C6H2)RuCl2}(m-1,8-dpmn)(Cp*RhCl2)]
(8c) (reddish brown, 73.4%): UVꢁ
/
Vis (CH2Cl2): lmax
4.0 Hz,
Cp*, 15H), 1.62 (s, 1- and 4-Me, 6H)*a, 1.64 (s, 1- and 4-
MeC6, 6H)*b, 2.05 (d, JPH
2.5Hz, 2- and 3-MeC6, 6H),
4.24 (d, JPH 3.0 Hz, PCH2, 4H), 4.36 (d, JPH 3.0 Hz,
PCH2, 4H), 4.54 (d, JPH 9.0 Hz, C6H, 2H), 4.93 (d,
JPH 9.0 Hz, C6H, 2H), 5.29 (s, CH2Cl2), 6.4ꢁ7.5 (m,
ArH, 26H). 31P{1H} NMR (CDCl3): d 33.6 (s, RuP),
35.9 (s, RuP), 39.3 (d, JRhP 143.0 Hz, RhP). Isomer
1
394 nm. H NMR (CDCl3): d 1.28 (d, JPH
ꢀ
/
giving yellow crystals of 11a (105.2 mg, 47.2%). UVꢁ
/
Vis
(CH2Cl2): lmax 360 nm. H NMR (CDCl3): d 0.80 (d,
JHH 6.5 Hz, i-Pr,
6.5 Hz, Me2C, 6H)*a, 0.82 (d, JHH
6H)*b, 1.61 (s, Me, 3H)*aꢂb, 2.20 (sep. JHH
6.5 Hz,
CH, 1H)*b, 2.45 (sep. JHH 6.5 Hz, CH, 1H)*a, 5.01 (d,
2JPH
9.5 Hz, PCH2, 2H), 5.15ꢁ5.85 (c, C6H4, 4H),
5.30 (s, CH2Cl2), 6.8ꢁ
8.0 (m, ArH, 10H). 31P{1H} NMR
(CDCl3): d 31.4 (s)*a, 39.0 (s)*b. Isomer ratio: C/Dꢀ
2.
1
ꢀ
/
ꢀ
/
ꢀ
/
ꢀ
/
ꢀ
/
ꢀ
/
ꢀ
/
ꢀ
/
ꢀ
/
/
ꢀ
/
/
/
ꢀ
/
/

80
Y. Yamamoto, F. Miyauchi / Inorganica Chimica Acta 334 (2002) 77ꢁ90
/
Calc. for C47H44P2ClSO3F3Ru×
/
0.25CH2Cl2: C, 58.77;
Calc. for C58H66NP2S2O6F6Rh: C, 57.76; H, 4.68; N,
1.16. Found: C, 57.11; H, 4.67;N, 1.32%.
H, 4.65. Found: C, 58.93; H, 4.56%.
The following cationic complexes were prepared
according to a procedure similar to 11a.
2.3. Preparation of Cl-bridged complexes
2.3.1. [{(p-Cymene)RuCl}2(m-1,8-dpmn)](OTf)2
(15a)
2.2.2. [(1,2,3-Me3C6H3)RuCl(1,8-dpmn)](PF6) (11b)
Reddish brown complex 11b (66.6 mg, 76.2%) was
obtained from [(1,2,3-Me3C6H3)RuCl2]2 (54.9 mg, 0.094
mmol), Ag(OTf) (56.5 mg, 0.220 mmol) and 1,8-dpmn
To a solution of 4a (221.8 mg, 0.195 mmol) in CH2Cl2
(15 ml) and acetone (5 ml) was added stirred at r.t. for
10 min. Ag(OTf) (70.2 mg, 0.273 mmol) was added
Ag(OTf) (116.8 mg, 0.455 mmol) at r.t.. After stirring
for 1 h, the solvent was removed and the residue was
extracted with CH2Cl2, followed by filtration through
the glass filter (G4). The CH2Cl2 was concentrated and
diethylether was added, giving brown crystals of 15a
(106.1 mg, 0.202 mmol). UVꢁ
302 nm. 1H NMR (CDCl3): d 1.43 (s, 1,3-MeC4, 3H)*a,
1.47 (s, 1,3-MeC4, 3H)*b, 2.15 (s, 2-MeC6, 3H)*aꢂb
4.02 (b, PCH2, 2H)*a or b, 4.84 (b, PCH2, 2H)*a or b, 5.28
(s, CH2Cl2), 6.4ꢁ
7.8 (m, ArH, 26H). 31P{1H} NMR
(CDCl3): d 32.0 (s)*a, 38.8 (s)*b. Isomer ratio: C/Dꢀ
50.
Calc. for C46H42P2ClSO3F3Ru×CH2Cl2: C, 55.60; H,
4.37. Found: C, 55.20; H, 4.33%.
/Vis (CH2Cl2): lmax 360,
,
/
/
(163.3 mg, 61.4%). FAB mass (m/z): 1214 ([{Mꢂ
CF3SO3)}ꢂl], 1067 (Mꢂl) (for Mꢀa cationic part).
UVꢁ
Vis (CH2Cl2): lmax 384, 306 nm. lH NMR (CDCl3):
/
/
/
/
/
/
d 1.27 (d, JHH
2.63 (sep. JHH
ꢀ6.0 Hz, Me2C, 6H), 1.60 (s, Me, 3H),
/
2.2.3. [Cp*RhCl(1,8-dpmn)](OTf) (12)
Yellow complex 12 (142.3 mg, 64.2%) was obtained
2
6.0 Hz, CH, 1H), 4.15 (d, JPH
ꢀ
/
ꢀ9.4
/
Hz, PCH2, 2H), 5.30 (s, CH2Cl2), 5.81, (b, C6H4, 4H),
6.8ꢁ
8.0 (m, ArH, 26H). 31P{1H} NMR (CDCl3): d 23.6
(s). Calc. for C58H58P2Cl2O6F6Ru2×CH2Cl2: C, 49.95;
H, 4.23. Found: C, 49.65; H, 4.23%.
from [Cp*RhCl2]2 (72.6 mg, 0.117 mmol), Ag(OTf) (70.2
mg, 0.273 mmol) and 1,8-dpmn (124.6 mg, 0.238 mmol).
/
/
1
UVꢁ
1.04 (t, JPH
15H)*b, 4.09 (b, PCH2, 2H)*a or b, 4.93 (b, PCH2, 2H)*a
or b, 5.28 (s, CH2Cl2), 6.4ꢁ
7.8 (m, ArH, 26H), Isomer
ratio: C/Dꢀ8 (at r.t.), C/Dꢀ50 (at ꢃ
40 8C). 31P{1H}
NMR (CDCl3): d 31.1 (d, JRhP
137 Hz)*a, 37.3 (d,
JRhP
137 Hz)*b. Calc. for C47H45P2ClSO3F3Rh×
/
Vis (CH2Cl2): lmax 363 nm. H NMR (CDCl3): d
ꢀ
/
3.5 Hz, 15H)*a, 1.05 (t, JPH
ꢀ3.5 Hz,
/
The following Cl-bridged complexes were prepared
according to a procedure similar to 15a.
/
/
/
/
2.3.2. [{Cp*RhCl}2(m-1,8-dpmn)](OTf)2 (16)
Reddish brown complex 16 (54.6 mg, 51.9%) was
obtained from 5 (87.8 mg, 0.077 mmol) and Ag(OTf)
ꢀ
/
ꢀ
/
/
0.5CH2Cl2: C, 57.65; H, 4.68. Found: C, 57.79; H,
4.80%.
(45.6 mg, 0.177 mmol). UVꢁ
1H NMR (CD2Cl2): d 1.40 (d, JPH
1.41 (d, JPH
3.3 Hz, 15H)*b, 4.0 (b, PCH2, 4H)*a or b
6.4ꢁ
7.9 (m, ArH, 26H). 31P{1H} NMR (CD2Cl2): d 34.4
(d, JRhH
152 Hz)*b, 36.5 (d, JRhH 148 Hz)*a. Calc.
1.5CH2Cl2: C, 47.73; H,
/
Vis (CH2Cl2): lmax 399 nm.
ꢀ
/
3.5 Hz, 15H)*a,
ꢀ
/
,
2.2.4. [Cp*IrCl(1,8-dpmn)](OTf) (13)
/
Yellow complex 13 (47.3 mg, 68.3%) was obtained
from [Cp*IrCl2]2 (53.2 mg, 0.067 mmol), Ag(OTf) (45.0
mg, 0.175 mmol) and 1,8-dpmn (72.3 mg, 0.140 mmol).
ꢀ
/
ꢀ
/
for C58H60P2Cl2S2O6F6Rh2×
/
4.24. Found; C, 47.76; H, 4.38%.
1
UVꢁ
1.03 (t, JPH
15H)*b, 4.41 (b, PCH2, 4H)*a or b, 5.0 (b, PCH2, 4H)*a
or b, 5.30 (b, CH2Cl2), 6.4ꢁ7.9 (m, ArH, 26H). 31P{1H}
NMR (CDCl3): d ꢃ
8.2 (s)*a, 1.46 (s)*b. Isomer ratio: C/
Dꢀ4. Calc. for C47H45P2ClSO3F3Ir 2CH2Cl2: C, 51.41;
/
Vis (CH2Cl2): lmax 303 nm. H NMR (CDCl3): d
ꢀ
/
3.5 Hz, 15H)*a, 1.04 (t, JPH
ꢀ3.5 Hz,
/
2.3.3. [{Cp*IrCl}2(m-1,8-dpmn)](OTf)2 (17)
Yellow complex 17 (23.7 mg, 22.0%) was obtained
from 6 (221.8 mg, 0.195 mmol) and Ag(OTf) (116.8 mg,
/
Vis (CH2Cl2): lmax 314 nm. 1H NMR
/
0.455 mmol). UVꢁ
(CD2Cl2): d 1.22 (d, JPH
4H), 6.4ꢁ
7.9 (m, ArH, 26H). 31P{1H} NMR (CD2Cl2):
d 13.1 (s). Calc. for C58H58P2Cl2S2O6F6Ir2×CH2Cl2; C,
43.38; H, 3.83. Found: C, 43.74; H, 3.89%.
/
/
ꢀ2.0 Hz, 30H), 4.63 (b, PCH2,
/
H, 4.22. Found: C, 51.42; H, 4.17%.
/
/
2.2.5. [Cp*Rh(1,8-dpmn)(MesNC)](OTf)2 (14)
After a solution of 12 (53.9 mg, 0.057 mmol) and
AgOTf (15.6 mg, 0.061 mmol) in CH2Cl2 (15 ml) and
acetone (5 ml) was stirred for 10 min at r.t., mesityl
isocyanide (14.3 mg, 0.094 mmol) was added. After 5 h,
the work-up similar to 11a gave pale yellow crystals of
2.3.4. [{Cp*RhCl(MesNC)}2(m-1,8-dpmn)](OTf)2
(18b)
A mixture of 16 (32.7 mg, 0.031 mml) and mesityl
isocyanide (MesNC) (13.4 mg, 0.092 mmol) was stirred
at r.t. After 5 h, the solution was concentrated and
diethyl ether was added, giving yellow crystals of 18b
14 (31.0 mg, 45.2%). IR (Nujol): 2141 cmꢃ1. UVꢁ
/
Vis
(CH2Cl2): lmax 302 nm. H NMR (CDCl3): d 1.44 (t,
JPH 3.5 Hz, 15H), 1.93 (s, o-Me, 6H), 2.39 (s, p-Me,
3H), 4.19 (b, PCH2, 4H), 6.4ꢁ7.9 (m, ArH, 28H).
31P{1H} NMR (CDCl3): d 41.9 (d, JRhH
122 Hz).
1
ꢀ
/
(16.7 mg, 32.3%). IR (Nujol): 2164 cmꢃ1. UVꢁ
/
Vis
(CH2Cl2): lmax 350 nm. H NMR (CDCl3): d 1.32 (d,
Jmꢀ3.5 Hz, 30H), 2.46 (s, p-Me, 6H), 2.51 (s, o-Me,
1
/
ꢀ
/
/

Y. Yamamoto, F. Miyauchi / Inorganica Chimica Acta 334 (2002) 77ꢁ
/90
81
12H), 4.25 (b, PCH2, 2H), 4.57 (b, PCH2, 2H), 6.4ꢁ
(m, ArH, 30H). 31P{1H} NMR (CD2Cl2): d 42.6 (d.
JRhP 126 Hz)). Calc. for C76H82N2P2Cl2S2O6F6Rh2:
C, 56.43; H, 4.98; N, 1.69. Found: C, 56.15; H, 5.01; N,
1.64%.
/
7.7
check of the stability of the crystals and no decay was
observed. Intensities were corrected for Lorentz and
polarization effects. The absorption correction was
made with the c scan method. Atomic scattering factors
were taken from Cromer and Waber the usual tabula-
tion [11]. Anomalous dispersion effects were included in
Fcalc [12]; the values of Df? and Dfƒ were those of
Creagh and McAuley [13]. All calculations were per-
formed using the TEXSAN crystallographic software
package [14].
ꢀ
/
2.3.5. [{Cp*RhCl(XylNC)}2(m-1,8-dpmn)](OTf)2
(18a)
Yellow complex 18a (13.5 mg, 28.8%) was obtained
from 16 (39.3 mg, 0.029 mmol) and xylyl isocyanide
(10.7 mg, 0.082 mmol). IR (Nujol): 2162 cmꢃ1. UVꢁ
/
Vis
(CH2Cl2): lmax 350 nm. H NMR (CDCl3): d 1.34 (d,
JPH 3.5 Hz, 30H), 2.34 (s, o-Me, 12H), 4.31 (b, PCH2,
2H), 4.92 (b, PCH2, 2H), 6.4ꢁ7.7 (m, ArH, 32H).
31P{1H} NMR (CDCl3): d 42.7 (d. JRhP
126 Hz).
Calc. for C76H78N2P2Cl2S2O6F6Rh2×0.5CH2Cl2: C,
1
2.5. Determination of the structures
ꢀ
/
/
The structures were solved by Patterson methods. The
positions of nonhydrogen atoms of complexes except a
carbon atom in 11a were refined with anisotropic
thermal parameters by using full-matrix least-squares
ꢀ
/
/
54.86; H, 4.75; N, 1.67. Found: C, 54.93; H, 4.81; N,
1.71%.
methods. All hydrogen atoms were calculated at the
˚
H distance of 0.95 A and not
refined.
ideal positions with the CÃ
/
2.3.6. [{Cp*IrCl(XylNC)}2(m-1,8-dpmn)](OTf)2
(19a)
This yellow complex (15.7 mg, 41.3%) was obtained
from 17 (32.5 mg, 0.021 mmol) and xylyl isocyanide (6.4
3. Results and discussion
mg, 0.049 mmol). IR (Nujol): 2155 cmꢃ1. UVꢁ
/
Vis
(CH2Cl2): lmax approximately 320(sh) nm. 1H NMR
(CDCl3): d 1.38 (d, JPH 2.5 Hz, 30H), 2.43 (s, o-Me,
7.6
3.1. Dinuclear complexes
ꢀ
/
12H), 4.45 (b, PCH2, 2H), 4.65 (b, PCH2, 2H), 6.4ꢁ
/
3.1.1. Homonuclear complexes
(m, ArH, 32H). 31P{1H} NMR (CDCl3): d 6.9 (s). Calc.
for C76H78N2P2Cl2S2O6F6Ir2: C, 50.41; H, 4.34; N, 1.55.
Found: C, 50.17; H, 4.47; N, 1.37%.
When 1,8-dpmn was treated with an equivalent of
[(h6-arene) RuCl2]2 (1) (a: p-cymene, b: l,2,3-Me3C6H3,
c: 1,2,3,4-Me4C6H2, d: 1,2,3,5-Me4C6H2, e: C6Me6) or
[Cp*MCl2]2 (2: Mꢀ
/
Rh, 3: Ir; Cp*ꢀC5Me5) at room
/
2.3.7. [{Cp*IrCl(MesNC)}2(m-1,8-dpmn)](OTf)2
(19b)
temperature, the Cl bridges cleave readily to give the
dinuclear complexes, [{(h6-arene)RuCl2}2(m-1,8-dpmn-
/
This yellow complex (10.2 mg, 28.0%) was obtained
from 17 (32.5 mg, 0.021 mmol) and xylyl isocyanide
P,P?)] (4) or [(Cp*MCl2)2(m-1,8-dpmn-P,P?)] (5: Mꢀ
Rh, 6: Ir) (Scheme 1). X-ray analysis of 5 revealed that
the Rh atom was surrounded by two Cl atoms and Cp*
ligand, and each Cp*RhCl2 moiety was connected by a
m-1,8-dpmp ligand (Fig. 1). Similar type of structures are
assumed for 4 and 6. The 1H NMR spectra of 4, 5, and 6
are in good agreement with the structure in the solid
state. In the 31P{1H} NMR spectra, the chemical shifts
appeared at d approximately 35 for 4, d 37.5 for 5, and
d 5.3 for 6, respectively (Fig. 2).
1
(mg, 0.049 mmol). IR (Nujol): 2155 cmꢃ1. H NMR
(CDCl3): d 1.37 (d, JPH
12H), 2.44 (s, p-Me, 6H), 4.42 (b, PCH2) 2H), 4.62 (b,
PCH2, 2H), 6.4ꢁ
7.7 (m, ArH, 32H). 31P{1H} NMR
ꢀ/2.5 Hz, 30H), 2.41 (s, o-Me,
/
(CDCl3): d 6.8 (s). Calc. for C78H82N2P2Cl2S2O6F6Ir2:
C, 50.95; H, 4.49; N, 1.52. Found: C, 50.66; H, 4.48; N,
1.68%.
2.4. Data collection
In an attempt to isolate mononuclear complex
(arene)RuCl2(1,8-dpmp-P), the reaction of 1a with 1,8-
dpmp was carried out in a 1:2 molar ratio, but was
unsuccessful to produce 4a as only isolabe complex
(Schemes 2 and 3).
Complexes, 5, 8b, 10, 11a, 12, 15a and 18b, were
recrystallized from CH2Cl2/ether. Cell constants were
determined from 20 reflections on Rigaku four-circle
automated diffractometer AFC5S. Data collections
were carried out by a Rigaku AFC5S refractometer at
3.1.2. Homonuclear complexes with different arene
groups
27 8C except ꢃ
along with data collections are summarized in Table 1.
Intensities were measured by the 2u ꢁv scan method
/
50 8C for 10. The crystal parameters
When 1a and 1b (or 1d) were treated with 2 equiv. of
1,8-dpmp at room temperature, brown complexes,
formulated as [{(p-cymene)RuCl2} (m-1,8-dpmn-
/
˚
0.71069 A). Throughout the
data collection the intensities of the three standard
using Mo Ka radiation (lꢀ
/
P,P?){(arene)RuCl2}] (7ab: areneꢀ/1,2,3-Me3C6H3;
reflections were measured every 200 reflections as a
7ad: areneꢀ1,2,3,5-Me4C6H2) were obtained selec-
/

Table 1
Crystal data of [(Cp*RhCl2)2(m-1,8-dpmp-P,P?)] (5), [(Cp*RhCl2)(m-1,8-dpmp-P,P?){(p-cymene)RuCl2}] (8b), [(Cp*RhCl2)(m-1,8-dpmp-P,P?)(Cp*IrCl2] (10), [{(p-cymene)RuCl}(l,8-dpmp-
P,P?)](OTf) (11a), [Cp*RhCI(1,8-dpmp-P,P?)](OTf) (12), [{(p-cymene)Ru(m-Cl)}2(m-1,8-dpmp-P,P?)](OTf)2 (15a), [{Cp*RhCl(MesNC)}2(m-1,8-dpmp-P,P?)](OTf)2 (18b)
Compound
5
8b
10
11a
12
15a
18
Formula
Molecular weight
Color
C56H62OP2Cl4Rh2 C55H57P2Cl4RuRh C59H66P2Cl10IrRh
1160.68
C47H44O3SP2CIF3Ru C47H45O3SP2ClF3Rh C58H58O6S2P2Cl2F6Ru2 C78H82O6S2P2Cl2F6Rh2
1125.79
yellow
1486.77
red
944.36
yellow
917.23
yellow
triclinic
1364.20
brown
1674.30
yellow
orange
monoclinic
P21/c(No 14)
Crystal system
Space group
monoclinic
P21/c (No 14)
monoclinic
P21/c (No 14)
monoclinic
P21/c (No 14)
monoclinic
C2/c (No15)
monoclinic
P21/n (No 14)
¯
P1 (No2)
/
Lattice parameters
˚
a (A)
˚
15.157(5)
14.886(6)
27.144(6)
90.0
11.548(7)
19.67(1)
21.817(7)
90.0
15.130(2)
14.931(4)
27.141(2)
90.0
11.608(6)
29.285(4)
12.869(5)
90.0
14.104(6)
14.663(5)
11863(4)
96.19(3)
105.84(4)
107.73(3)
2198(1)
2
24.213(9)
17.410(8)
16.482(2)
27.511(3)
17.346(2)
90.0
b (A)
˚
c (A)
16.899(7)
90.0
a (8)
b (8)
97.47(2)
90.0
90.96(4)
90.0
96.437(10)
90.0
100.23(3)
90.0
125.08(2)
90.0
5830(4)
99.37(1)
90.0
g (8)
3
V (A )
˚
6072(3)
4
4955(3)
4
6092(1)
4
1.621
4304(2)
4
7760(1)
4
Z
4
1.552
8.04
Dcalc (g cmꢃ3
)
1.269
8.04
1.509
9.54
1.457
6.03
1.431
6.21
1.433
6.55
m (cmꢃ1
)
29.86
16
13996
Scan rate (8 per min)
Number of reflections (u B508) 11127
Number of data used
Number of variables
R; Rw
8
8
8731
8
7588
16
7740
8
5127
8
13670
13670
901
4581 (I ꢀ3.0s(I)) 3903 (I ꢀ2.5s(I)) 10821 (I ꢀ3.0s(I)) 7588
586
7740
523
3036 (I ꢀ2.0s(I))
353
568
636
0.051; 0.081
513
a
b
a
b
b
b
b
0.090; 0.132
0.090(4581)
1.81
0.118; 0.180
0.065 (3903)
1.42
0.169; 0.215
0.066 (3903)
1.22
0.121; 0.193
0.061 (6011)
1.87
0.137; 0.181
0.070(3036)
1.37
0.112; 0.160
0.056 (10317)
1.31
R1 (reflections)
c
GOF
0.051 (10821)
1.82
a
RꢀR1ꢀajjFojꢃjFcjj/ajFoj and Rwꢀ[aw(½FojꢃjFcj)2/awjFoj ] (wꢀ1/s2(Fo)).
2 1/2
b
c
2
Rꢀa(Fo2ꢃFc2)/aFo and Rw ꢀ[aw(Fo2ꢃFc2)2/aw(Fo2)2]1/2(wꢀ1/s2(Fo)). R1ꢀajjFojꢃjFcjj/a½Foj for I ꢀ2.0s(I).
GOFꢀ[aw(½Fojꢃ½Fcj)2/(NobsꢃNparm)]1/2
.

Y. Yamamoto, F. Miyauchi / Inorganica Chimica Acta 334 (2002) 77ꢁ
/90
83
Scheme 1. Reaction of 1,8-dpmp with [(arene)RuCl2]2 or [Cp*MCl2]2 (MꢀRh, Ir).
/
nances at d 31.5 and 32.2 were assigned to the former,
and the resonances at d 36.2 and 38.8 were assigned to
the latter on the basis of comparison with the chemical
shift values of 1a and 1b. The 31P{1H} NMR spectrum
of 7ad showed two singlets for the P atom connected by
the (p-cymene)Ru group, whereas it showed only one
singlet at d 35.8 for another P atom, probably being due
to an accidental degeneracy of chemical shifts. Two
conformational structures are assumed for the isomers
as depicted in Fig. 2; (A) each metal moeity lies on the
opposite side through the naphthalene framework and
(B) a metal moiety lies on the same side as another metal
one. The conformer A, confirmed by X-ray analysis, is
sterically more stable than the conformer B. Thus, the
isomer ratios A/B derived from the NMR spectra are 1.3
for 7ab and 1.8 for 7ad, respectively.
Reactions of 1a with 1e gave only 4a and 4e bearing
the same arenes ring without formation of the complex
with different arene rings. There is no information to
control the reaction path.
Fig. 1. Molecular structure of [(Cp*RhCl2)2(mÃ1,8-dpmp-P,P?)] (5).
/
3.1.3. Heteronuclear complexes
1
tively. In the H NMR spectra, the methyl resonances
for i-propyl group were observed as two sets of
doublets, suggesting the presence of isomers. In fact,
the 31P{1H} NMR spectrum of 7ab showed two sets of
singlets for the P atoms connected by the (p-cymene)Ru
and (1,2,3-Me3C6H3)Ru groups, respectively; the reso-
Reactions of 2 with 1a, 1b or 1e were carried out in
the presence of 1,8-dpmp giving the heteronuclear
complexes [(Cp*RhCl2)(m-1,8-dpmn-P,P?) {(arene)R-
uCl2}] (areneꢀp-cymene (8a), 1,2,3-Me3C6H3 (8b);
/
1,2,3,4-Me4C6H2 (8c)) bearing Rh(III) and Ru(II)
atoms. Heteronuclear complexes bearing Ir(IlI) and
Scheme 2. Preparation of homonuclear complexes bearing different arene rings and heteronuclear complexes.

84
Y. Yamamoto, F. Miyauchi / Inorganica Chimica Acta 334 (2002) 77ꢁ90
/
Scheme 3. Preparation of ionic complexes (PSPꢀ
1,8-dpmn-P,P?).
/
Fig. 2. Conformation of coordinated 1,8-dpmp in dimeric complexes.
Ru(II) atoms, and Ir(III) and Rh(IIl) atoms,
[(Cp*IrCl2)(m-1,8-dpmn-P,P?){(arene)RuCl2}] (areneꢀ
/
p-cymene (9a), 1,2,3-Me3C6H3 (9b) and [(Cp*RhCl2)(m-
1,8-dpmn-P,P?)(Cp*IrCl2)] 10 were also generated from
the corresponding complexes. It was confirmed by X-ray
analyses of 8b and 10 that the molecular structures are
fundamentally similar to that for 5 (Figs. 3 and 4), Thus,
complex 9 is assumed to have a structure similar to 10.
1
In the H NMR spectra, complexes 8 and 9 showed
the presence of isomers in solution, whereas 10 has
similar structure in solution and the solid state. For
example, the 1H NMR spectrum of 9b in CD2C12
showed two doublets at d 1.25 and 1.26 due to Cp*
protons, two doublets at d 1.90 and 1.91 due to 1- and 3-
methyl protons on the arene ring and two doublets at d
2.07 and 2.08 due to 2-methyl protons on the arene ring.
Fig. 3. Molecular structure of [(Cp*RhCl2)(m-1,8-dpmp){(1,2,3-Me3-
C6H3)RuCl2}] (8b).
In the 31P{1H} NMR spectrum, four singlets appeared
at d 5.67, 6.54, 34.5 and 35.5. The two singlets at d 5.67
and 6.54 are due to the P atom connected by the Ir
atom, and two singlets at d 34.5 and 35.5 are due to the

Y. Yamamoto, F. Miyauchi / Inorganica Chimica Acta 334 (2002) 77ꢁ
/90
85
Fig. 4. Molecular structure of [(Cp*RhCl2)(m-1,8-dpmp)(Cp*IrCl2)]
(10).
P atom connected by Ru atom on the basis of the
chemical shift values of 4b and 6. The isomer ratio A/B
is 4.7. Based on NMR spectra, the apparent isomer
ratios A/B are estimated as 1.8 for 8a, 1.2 for 8b, 6.5 for
8c, and 3.1 for 9a, respectively.
Fig. 5. Molecular structure of [(p-cymene)RuCl(m-1,8-dpmp-
P,P)](OTf) (11a).
3.2. Ionic complexes
Reactions of 1a or 1b with 2 equiv. of 1,8-dpmn were
carried out in the presence of AgOTf, giving the ionic
complexes, [(arene)RuCl(1,8-dpmn-P,P?)](OTf) (11)
(areneꢀ
type of rhodium and iridium complexes, [Cp*MCl(1,8-
dpmn-P,P?)] (OTf) (12: MꢀRh; 13: MꢀIr) were
/p-cymene (a); 1,2,3-Me3CeH3 (b)). The similar
/
/
obtained from the reactions of 2 or 3 with 1,8-dpmn.
1
The presence of isomers was observed by the H and
31P{1H} NMR spectra. The 31P{1H} NMR spectrum of
12 in a mixture of CD2Cl2 and CD3COCD3 (1:1) showed
two doublets at d 33.4 and 39.1 in an intensity ratio of
1:8 at room temperature. The isomer ratio decreased
with cooling and was approximately 1:50 at ꢃ45 8C.
/
Fig. 6. Molecular structure of [Cp*RhCl(m-1,8-dpmp-P,P?)](OTf)
(12).
In order to examine the detailed structure, X-ray
analyses of 11a and 12 were performed (Figs. 5 and 6).
The Cl atom and the naphthalene ring lie on the same
side of the P2C2 plane and then the Cl atom points
towards the centroid of the naphthalene ring as depicted
in Fig. 7 (isomer C). Another isomer (D) is assumed that
the Cl atom locates on the opposite side as the
naphthalene ring. This conformation (D) is assumed to
be more unstable than C, since it has steric repulsion
between the phenyl rings and the Cl atom. Therefore,
the isomer C is assignable to the complex having the
structure confirmed by X-ray analyses. Based on the
31P{1H} NMR spectra, the apparent isomer ratios C/D
in CDCl3 are 2 for 11a, 50 for 11b and 4 for 13,
respectively.
Fig. 7. Conformers of ionic complexes 11,12, 13.and 14.
The conformer C is assumed to be superior to D by the
steric demand of the bulky isocyanide ligand.
Dimeric complex 4a was treated with 2 equiv. of
AgOTf, giving the brown complex formulated as [{h6-p-
When 12 was treated with mesityl isocyanide in the
presence of Ag(OTf), pale yellow complex [Cp*Rh(1,8-
dpmn-P,P?)(MesNC)](OTf) (14) was generated. No
isomers were observed from the NMR spectroscopy.

86
Y. Yamamoto, F. Miyauchi / Inorganica Chimica Acta 334 (2002) 77ꢁ90
/
cymene)RuCl}2(m-1,8-dpmn)](OTf)2 (15a). In the FAB
MS, the ion fragments centered around m/z 1214 and
1067 were estimated to be the [Mꢂ
/
TfOꢂ
/
l]ꢂ and [Mꢂ
/
l]ꢂ (Mꢀcationic part), respectively. The 1H NMR
/
spectrum showed a doublet at d 1.27, a singlet at d
2.01 and a septet at d 2.63 due to methyl protons of
isopropyl group, methyl protons and methine proton,
respectively. In the 31P{1H} NMR spectrum a singlet
appeared at d 23.6. The spectroscopic data suggested
the Cl-bridged structure. The X-ray analysis supported
the proposed structure (Fig. 8). The similar type of
rhodium and iridium complexes, [(Cp*MCl)2(1,8-dpmn-
P,P?)](OTf)2 (16: Mꢀ
/
Rh; 17: MꢀIr), were generated
/
by the reactions of 5 or 6 with Ag(OTf).
Complexes 16 and 17 reacted readily with isocyanide
to give the isocyanide complexes [{Cp*MCl(RHC)}2-
(1,8-dpmn-P,P?)](OTf)2 (18a: Mꢀ
MꢀRh, RꢀMes; 19a: MꢀIr, Rꢀ
RꢀMes). Complex 19a was prepared by the direct
/
Rh, Rꢀ
/
Xyl; 18b:
/
/
/
/
Xyl; 19b: Mꢀ
/Ir,
/
reaction of [Cp*IrCl2(XylNC)] with 0.5 equiv. of 1,8-
1
dpmn in the presence of 2 equiv. of Ag(OTf). The H
Fig. 9. Molecular structure of [{Cp*RhCl(MesNC)}2(m-1,8-dpmp-
P,P?)](OTf)2 (18b).
NMR spectra showed a set of resonances for isocyanide
and arene ring, suggesting a symmetric structure. The X-
ray analysis of 18b also confirmed the proposed
structure (Fig. 9).
3.3.1. Structure of 5
A perspective drawing of 5 with an atomic numbering
scheme is given in Fig. 1, and selected bond lengths and
angles are listed in Table 2. The molecule has a dimeric
structure connected by a m-1,8-dpmp ligand, and the
rhodium atoms are surrounded by two Cl atoms and a P
atom. The Cp*Rh moiety occupies each side of the
naphthalene ring and the Rh(l)ꢀ ꢀ ꢀRh(2) and P(l)ꢀ ꢀ ꢀP(2)
3.3. Molecular structures
Detailed discussion of distances and angles is avoided
here because of the low accuracy of the X-ray data,
˚
distances are separated by 8.91 and 5.82 A, respectively.
˚
The closest Cl(2) and Cl(3) separation is 5.72 A. The XÃ
/
especially the CÃ
/
C bond lengths, for 5, 8b, and 15b, but
the tables of selected bond lengths and angles are given.
RhÃ
/
Y angles around the Rh atoms are in the range
from 86 to 938. The average RhÃ
/
Cl and RhÃP bond
/
˚
lengths are 2.406 and 2.332 A, respectively.
3.3.2. Structure of 8b
A perspective drawing of 8b with an atomic number-
ing scheme is given in Fig. 3, and selected bond lengths
and angles are listed in Table 3. The molecule has a
dimeric structure connected by a m-1,8-dpmp ligand, and
the rhodium atoms are surrounded by two Cl atoms and
a P atom. The Cp*RhCl2 and (1,2,3-Me3C6H3)RuCl2
moieties mutually lies on the both sides of the naphtha-
lene ring. The Rh(1)ꢀ ꢀ ꢀRu(1) and P(1)ꢀ ꢀ ꢀP(2) distances
˚
are separated by 7.34 and 5.95 A, respectively. The
˚
former is approximately 1.5 A shorter than that of the
˚
parent complex 5c and the latter is approximately 0.1 A
longer. The closest Cl(2)ꢀ ꢀ ꢀCl(3) and Cl(2)ꢀ ꢀ ꢀCl(4)
˚
separations are 6.97 A, approximately 1.0 A longer
˚
than that found in 5c. The XÃ
/
RhÃ
/
Y angles around the
Rh atoms are in the range from 86 to 948, and those
around the Ru atoms are in the range from 85 to 948.
Fig. 8. Molecular structure of [{(p-cymene)Ru(m-Cl)}2(m-1,8-dpmp-
P,P?)](OTf)2 (15a).
˚
The average RhÃ
/
Cl bond length of 2.395 A and the RhÃ
/

Y. Yamamoto, F. Miyauchi / Inorganica Chimica Acta 334 (2002) 77ꢁ
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87
Table 2
1
˚
Selected bond lengths (A) and angles (8) of [(Cp*RhCl2)2(1,8-dpmn-P,P )] 5
Bond lengths
Rh(1)ÃCl(1)
Rh(2)ÃCl(3)
P(1)ÃC(45)
C(54)ÃC(56)
Rh(1)ꢀ ꢀ ꢀRh(2)
C1(1)ꢀ ꢀ ꢀC1(4)
2.400(6)
2.412(5)
1.85(2)
1.56(2)
8.91
Rh(1)ÃCl(2)
Rh(2)ÃCl(4)
P(2)ÃC(56)
2.409(6)
2.404(6)
1.86(2)
Rh(1)ÃP(1)
Rh(2)ÃP(2)
C(45)ÃC(46)
2.332(5)
2.331(5)
1.54(3)
P(1)ꢀ ꢀ ꢀP(2)
5.82
5.72
Cl(1)ꢀ ꢀ ꢀCl(3)
C(2)ꢀ ꢀ ꢀCl(4)
8.41
8.38
10.22
Cl(2)ꢀ ꢀ ꢀCl(3)
Bond angles
Cl(1)ÃRh(1)ÃCl2
Rh(1)ÃP(1)ÃC(45)
P(2)ÃC(56)ÃC(54)
93.1(2)
109.5(7)
115.0(1)
Cl(1)ÃRh(1)ÃP(1)
P(1)ÃC(45)ÃC(46)
89.4(2)
114.0(1)
Cl(2)ÃRh(1)ÃP(1)
Rh(2)ÃP(2)ÃC(56)
86.4(2)
111.6(6)
Table 3
˚
Selected bond lengths (A) and angles (8) of [(Cp*RhCl2)(1,8-dpmn-P,P?){(1,2,3-Me3C6H3)RuCl2}] (8b)
Bond lengths
Rh(1)ÃCl(1)
Ru(1)ÃCl(3)
P(1)ÃC(23)
C(32)ÃC(34)
Rh(1)ꢀ ꢀ ꢀRu(1)
Cl(1)ꢀ ꢀ ꢀCl(4)
2.381(4)
2.397(4)
1.87(1)
1.49(2)
7.34
Rh(1)ÃCl(2)
Ru(1)ÃCl(4)
P(2)ÃC(34)
2.407(4)
2.412(4)
1.86(1)
Ru(1)ÃP(1)
Ru(1)ÃP(2)
C(23)ÃC(24)
2.349(4)
2.356(4)
1.52(2)
P(1)ꢀ ꢀ ꢀP(2)
5.95
6.97
Cl(1)ꢀ ꢀ ꢀCl(3)
C(2)ꢀ ꢀ ꢀCl(4)
9.58
6.97
9.69
Cl(2)ꢀ ꢀ ꢀC1(3)
Bond angles
Cl(1)ÃRh(1)ÃCl(2)
Rh(1)ÃP(1)ÃC(23)
Cl(3)ÃRu(1)ÃP(2)
P(2)ÃC(34)ÃC(32)
89.4(2)
113.1(5)
84.9(1)
Cl(1)ÃRh(1)ÃP(1)
P(1)ÃC(23)ÃC(24)
Cl(4)ÃRu(1)ÃP(2)
86.5(1)
116.2(10)
93.9(1)
Cl(2)ÃRh(1)ÃP(1)
Cl(3)ÃRu(1)ÃCl(4)
Ru(1)ÃP(2)ÃC(34)
89.6(1)
89.6(2)
116.5(5)
117.4(9)
Table 4
˚
Selected bond lengths (A) and angles (8) of [(Cp*RhCl2)(1,8-dpmn-P,P?)(Cp*IrCl2)] (10)
Bond lengths
M(1)ÃCl(1)
M(2)ÃCl(3)
P(1)ÃC(21)
C(30)ÃC(32)
2.405(1)
2.410(1)
1.879(5)
1.503(7)
M(1)ÃCl(2)
M(2)ÃCl(4)
P(2)ÃC(32)
2.414(1)
2.411(2)
1.886(1)
M(1)ÃP(1)
M(2)ÃP(2)
C(21)ÃC(22)
2.316(1)
2.317(1)
1.524(7)
Bond angles
Cl(1)ÃM(1)ÃCl(2)
Cl(3)ÃM(2)ÃCl(4)
M(1)ÃP(1)ÃC(21)
P(2)ÃC(32)ÃC(30)
91.54(1)
92.36(6)
112.2(2)
115.5(4)
Cl(1)ÃM(1)ÃP(1)
Cl(3)ÃM(2)ÃP(2)
P(1)ÃC(21)ÃC(22)
89.01(5)
85.55(5)
114.8(3)
Cl(2)ÃM(1)ÃP(1)
Cl(4)ÃM(1)ÃP(2)
M(2)ÃP(2)ÃC(32)
85.31(4)
88.53(5)
111.4(2)
Table 5
˚
Selected bond lengths (A) and angles (8) of [(p-cymene)RuCl (1,8-dpmn-P,P?)](OTf) (11a)
Bond lengths
Ru(1)ÃCl(1)
P(1)ÃC(35)
C(44)ÃC(46)
2.388(2)
1.849(9)
1.51(1)
Ru(1)ÃP(1)
P(2)ÃC(46)
2.355(3)
1.869(9)
Ru(1)ÃP(2)
C(35)ÃC(36)
2.342(2)
1.52(1)
Bond angles
Cl(1)ÃRu(1)ÃP(1)
Ru(1)ÃP(1)ÃC(35)
C(36)ÃC(45)ÃC(44)
P(2)ÃC(46)ÃC(44)
88.12(9)
123.5(3)
126.7(9)
119.0(6)
Cl(1)ÃRu(1)ÃP(2)
P(1)ÃC(35)ÃC(36)
C(45)ÃC(44)ÃC(46)
83.99(8)
117.2(6)
126.6(9)
P(1)ÃRu(1)ÃP(2)
C(35)ÃC(36)ÃC(45)
Ru(1)ÃP(2)ÃC(46)
94.60(9)
126.9(9)
122.0(3)

88
Y. Yamamoto, F. Miyauchi / Inorganica Chimica Acta 334 (2002) 77ꢁ90
/
the neutral complexes. The PÃ
94.60(9)8 for 11a and 96.04(5)8 for 12, compared with
those of [MCl2(1,8-dpmn)] (MꢀPd, Pt), [M2(1,8-
dpmn)(MesNC)4](PF6)2 (MꢀPd, Pt), [Pd2(1,8-
/
RuÃ/P bite angles are
/
/
dpmn)2(MesNC)2](PF6)2 and RuH2(CO)(PPh3)(1,8-
dpmn).
3.3.5. Structure of 15a
A perspective drawing with an atomic numbering
scheme is given in Fig. 8, and selected bond lengths and
angles are listed in Table 7. The molecule has crystal-
lographic twofold symmetry and sits astride a twofold
axis making one-half of the complex unique. The
complex cation consists of two ruthenium atoms bridged
by two Cl atoms and a 1,8-dpmp ligand with Ruꢀ ꢀ ꢀRu*
˚
˚
separation of 3.71 A and Clꢀ ꢀ ꢀCl* separation of 3.14 A.
These separations are compared with those (Rhꢀ ꢀ ꢀRhꢀ
/
˚
˚
3.28 A) found in tetranuclear
3.68 A and Clꢀ ꢀ ꢀClꢀ
/
complex [{Cp*Rh(m-Cl)}4(pyrazine)2](OTf)4 [15]. One
methyl-carbon atom of the isopropyl group lies above
the benzene ring plane and a similar behavior is
observed in 11a, whereas two methyl-carbon atoms of
the isopropyl group sit on the benzene ring plane. The
Ru(1)P(1)C(23)C(24) and P(1)C(23)C(24)C(29) torsion
Fig. 10. Framework of [{Ru(m-Cl)}2(m-1,8-dpmn-P,P?)] in 15a.
˚
P length of 2.332 A is not significantly different from the
˚
˚
P length of 2.354 A,
RuÃ
/
Cl one of 2.405 A and the RuÃ
/
respectively.
angles are ꢃ
/
162 and ꢃ908, respectively. The naphtha-
/
lene ring is perpendicular to the rhombus
Ru(1)Cl(1)Ru(1)*Cl(1)* lying on the position near the
two middle points of the Ru(1) and Cl(1) atoms and of
3.3.3. Structures of 10
A perspective drawing of 10 with an atomic number-
ing scheme is given in Fig. 4, and selected bond lengths
and angles are listed in Table 4. Compound 10 was
analyzed as a structure that two metal atoms have a Rh/
Ir occupancy of 0.5. The structure is fundamentally
similar to that for 5 or 8b. Two metals are separated by
the Ru(1)* and Cl(1)* atoms (Fig. 10). The RuÃ
/
Clbr and
˚
˚
ꢄ
RuÃ
respectively, compared with the RuÃ
P(1) bond length of 2.396 A
/
Clbr bond lengths are 2.439(3) A and 2.459(3) A,
/Clterm bond lengths
˚
for 8b and 11a. TheRu(1)Ã
/
is longer than those found in 8b and 11a, suggesting the
steric strain of a four-ring structure.
˚
8.90 A, compared with the Rhꢀ ꢀ ꢀRh separation in 5. The
average metalÃ
/
Cl and metalÃ
/P bond lengths are 2.410
˚
˚
A and 2.316 A, respectively, compared with those found
in 5.
3.3.6. Structures of 18b
A perspective drawing with an atomic numbering
scheme is given in Fig. 9, and selected bond lengths and
angles are listed in Table 8. Each rhodium atom is
surrounded by Cl and P atoms, and terminal carbon
atom of isocyanide ligand. Each rhodium moiety located
mutually on the both sides of the naphthalene ring with
3.3.4. Structure of 11a and 12
Perspective drawings with the atomic numbering
schemes are given in Figs. 5 and 6, and selected bond
lengths and angles are listed in Tables 5 and 6. The
average lengths of the RuÃ
/
P and RhÃ
/
P bond are 2.349
and 2.348 A, respectively, compared with those found in
˚
˚
the Rhꢀ ꢀ ꢀRh separation of 7.44 A, being shorter by
Table 6
˚
Selected bond lengths (A) and angles (8) of [(Cp*RhCl (1,8-dpmn-P,P?)](OTf) (12)
Bond lengths
Rh(1)ÃCl(1)
P(1)ÃC(35)
C(44)ÃC(46)
2.387(2)
1.867(6)
1.511(9)
Rh(1)ÃP(1)
P(2)ÃC(46)
2.352(2)
1.859(9)
Rh(1)ÃP(2)
C(35)ÃC(36)
2.344(2)
1.513(9)
Bond angles
Cl(1)ÃRh(1)ÃP(1)
Ru(1)ÃP(1)ÃC(35)
C(36)ÃC(45)ÃC(44)
P(2)ÃC(46)ÃC(44)
88.29(5)
120.9(2)
127.3(5)
120.7(4)
Cl(1)ÃRu(1)ÃP(2)
P(1)ÃC(35)ÃC(36)
C(45)ÃC(44)ÃC(46)
87.17(6)
117.2(4)
125.6(5)
P(1)ÃRu(1)ÃP(2)
C(35)ÃC(36)ÃC(45)
Ru(1)ÃP(2)ÃC(46)
96.04(5)
126.7(6)
122.6(2)

Y. Yamamoto, F. Miyauchi / Inorganica Chimica Acta 334 (2002) 77ꢁ
/90
89
Table 7
˚
Selected bond lengths (A) and angles (8) of [{(p-cymene)Ru(m-Cl)}2(m-1,8-dpmn-P,P?)](OTf)2 (15a)
Bond lengths
Ru(1)ÃCl(1)
P(1)ÃC(23)
P(1)ÃC(17)
2.439(3)
1.86(1)
1.83(1)
Ru(1)ÃCl(1)*
C(23)ÃC(24)
2.459(3)
1.48(1)
Ru(1)ÃP(1)
P(1)ÃC(11)
2.396(3)
1.833(10)
Bond angles
Cl(1)ÃRu(1)ÃCl(1)*
Rh(1)ÃCl(1)ÃRu(1)*
Ru(1)ꢀ ꢀ ꢀRu(1)*
79.78(9)
98.56(9)
3.71
Cl(1)ÃRu(1)ÃP(1)
Ru(1)ÃP(1)ÃC(23)
P(1)ꢀ ꢀ ꢀP(1)*
91.01(9)
113.2(3)
4.60
Cl(1)*ÃRu(1)ÃP(1)
P(1)ÃC(23)ÃC(24)
Cl(1)ꢀ ꢀ ꢀCl(1)*
91.57(9)
121.5(7)
3.14
Table 8
˚
Selected bond lengths (A) and angles (8) of [{Cp*RhCl(MesNC)}2(m-1,8-dpmn-P,P?)](OTf) (18b)
Bond lengths
Rh(1)ÃCl(1)
P(1)ÃC(33)
Rh(2)ÃCl(2)
P(2)ÃC(44)
Rh(1)ꢀ ꢀ ꢀRh(2)
2.395(1)
1.854(1)
2.400(1)
1.868(4)
7.44
Rh(1)ÃP(1)
C(33)ÃC(34)
Rh(2)ÃP(2)
C(42)ÃC(44)
P(1)ꢀ ꢀ ꢀP(2)
2.326(1)
1.490(6)
2.340(1)
1.509(6)
5.54
Rh(1)ÃC(11)
C(11)ÃN(1)
Rh(2)ÃC(67)
C(67)ÃN(2)
Cl(1)ꢀ ꢀ ꢀCl(2)
1.962(4)
1.144(5)
1.964(5)
1.156(6)
5.78
Bond angles
Cl(1)ÃRh(1)ÃP(1)
Rh(1)ÃP(1)ÃC(33)
C(11)ÃN(1)ÃC(12)
Cl(2)ÃRu(2)ÃP(2)
Ru(2)ÃP(2)ÃC(44)
C(11)ÃN(1)ÃC(12)
90.03(4)
110.5(1)
167.9(5)
89.85(4)
111.4(1)
167.9(5)
Cl(1)ÃRh(1)ÃC(11)
P(1)ÃC(33)ÃC(34)
88.8(1)
114.8(3)
P(1)ÃRu(1)ÃC(11)
Rh(1)ÃC(11)ÃN(1)
91.0(1)
169.9(4)
Cl(2)ÃRu(2)ÃC(67)
P(2)ÃC(44)ÃC(42)
84.2(1)
116.8(3)
P(2)ÃRu(2)ÃC(67)
Ru(2)ÃC(67)ÃN(2)
93.7(1)
168.3(4)
˚
approximately 1.5 A than that in the parent complex 5,
Takahashi, Professor Kiyotaka Onizuka, and Dr. Fumie
Takei of the Institute of Scientific and Industrial
Research, Osaka University, for X-ray analysis and
measurements of FAB MS.
˚
whereas the Pꢀ ꢀ ꢀP separation of 5.44 A is not different.
The RhÃ
/
CÃ
/
N and CÃ
/
NÃ
/
C angles are nearly linear with
approximately 1708. The RhÃ
/
P, RhÃ
/
Cl and RhÃ
/C
bond lengths are in usual values.
The torsion angles of the naphthalene ring in m-
coordinated complexes 5, 8b, 10 and 18b are approxi-
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in 11a is ꢃ1.78. These data indicated the presence of the
/
158, whereas those in chelating complexes 11a
/
28. For example, the torsion
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