Scope and diastereoselectivity of intramolecular [4 + 2] Diels-Alder cycloaddition reactions of (η6-arene)Ru(DMPP)Cl2 complexes with dieneophilic ligands

Article abstract of DOI:10.1016/S0022-328X(00)00504-0

The complexes (η⁶-arene)Ru(DMPP)Cl₂ (DMPP = 3,4-dimethyl-1-phenylphosphole; arene = C₆H₆, MeC₆H₅, p-MeC₆H₄CHMe₂, and C₆Me₆) react with

Full text of DOI:10.1016/S0022-328X(00)00504-0

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 613 (2000) 177–199
Scope and diastereoselectivity of intramolecular [4+2]
Diels–Alder cycloaddition reactions of (h6-arene)Ru(DMPP)Cl2
complexes with dieneophilic ligands
Kent D. Redwine, John H. Nelson *
Department of Chemistry/216, College of Arts and Science, Uni6ersity of Ne6ada, Reno, NV 89577-0020, USA
Received 28 March 2000; received in revised form 22 May 2000
Abstract
The complexes (h6-arene)Ru(DMPP)Cl2 (DMPP=3,4-dimethyl-1-phenylphosphole; arene=C6H6, MeC6H5, p-
MeC6H4CHMe2, and C6Me6) react with NaPF6 and the dieneophilic ligands: Ph2PCHꢀCH2 (DPVP), Me2NC(O)CHꢀCH2
(DMAA), MeC(O)CHꢀCH2 (MVK), PhSCHꢀCH2 (PVS), PhS(O)CHꢀCH2 (PVSO), and 2-vinylpyridine (2VP) to produce
[(h6-arene)Ru(syn-exo-2-R-5,6-dimethyl-7-phenyl-7-phosphabicyclo [2.2.1] hept-5-ene)Cl]PF6 complexes (R=ꢁPPh2, ꢁC(O)NMe2,
ꢁC(O)Me, ꢁPhS, ꢁPhS(O), and ꢁ2C5H4N, respectively) with high diastereo-selectivities. Similar reactions of (h6-
arene)Ru(DMPP)Cl2 with NaPF6 and allyldiphenyl-phosphine (ADPP) produced the mixed ligand complexes [(h6-
arene)Ru(DMPP) (ADPP)Cl2]PF6 which did not undergo subsequent [4+2] Diels–Alder cycloadditions even at elevated
temperatures. New complexes were characterized by elemental analyses, physical properties, cyclic voltammetry, infrared
spectroscopy, 1H-, 1H{31P}-, 13C{1H}-, and 31P{1H}-NMR spectroscopy and in most cases by X-ray crystallography. © 2000
Elsevier Science B.V. All rights reserved.
Keywords: Phosphole; [4+2] Diels–Alder cycloaddition; Ruthenium; X-ray crystallography
1. Introduction
We have employed the highly efficient and
diastereoselective [4+2] Diels–Alder cyclo-addition re-
actions of 1H-phospholes [1] and 2H-phospholes [2]
with a variety of dieneophiles for the synthesis of a
number of conformationally rigid asymmetric chelating
ligands. Typical reactions of three-legged piano stool
complexes of 3,4-dimethyl-1-phenylphosphole (DMPP)
are illustrated in reactions 1–3.
Because these reactions occur intramolecularly,
within the coordination sphere of a transition metal, of
the four possible diastereomers, only the syn-exo
diastereomer of the 2-R-5,6-dimethyl- 7-phenyl-7-phos-
phabicyclo [2.2.1] hept-5-ene is formed [1] (Chart 1).
* Corresponding author. Tel.: +1-775-7846588; fax: +1-775-
7846804.
E-mail address: jhnelson@equinox.unr.edu (J.H. Nelson).
0022-328X/00/$ - see front matter © 2000 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(00)00504-0

178
K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
on a Mel-Temp apparatus and are uncorrected. NMR
spectra were recorded on acetone-d6 or nitromethane-d3
solutions with a Varian Unity Plus-500 FT spectrometer
operating at 500 MHz for 1H, 202 MHz for 31P, and 125
MHz for 13C. Proton and carbon chemical shifts were
referenced to residual solvent resonances and phosphorus
chemical shifts were referenced to an external 85%
aqueous solution of H3PO4. All shifts to low field, high
frequency are positive. FT-IR spectra were recorded as
Nujol mulls on CsI windows on a Perkin–Elmer BX
spectrometer. Cyclic voltammograms were recorded at
25°C in freshly distilled CH2Cl2 containing 0.1 M tetra-
butylammonium hexafluorophosphate using a BAS
CV50-W voltammetric analyzer. A three electrode system
was used. The working electrode was a platinum disk, the
auxiliary electrode was a platinum wire, and the reference
electrode was Ag–AgCl (aqueous) separated from the cell
by a Luggin capillary. The Fc/F+c couple occured at 480
mV under the same conditions.
Chart 1.
Recently, organopalladium complexes containing opti-
cally pure forms of orthopalladated (1-(dimethyl-
amino)ethyl)naphthalene [3] and (2-(dimethylamino)-
ethyl)naphthalene [4] have been used as chiral templates
to promote asymmetric modifications of these Diels–
Alder cycloaddition reactions with several dieneophilic
ligands.
In general these reactions do not occur in the absence
ofatransitionmetal. [5]Thescopeanddiastereoselectivity
of these transition metal promoted intramolecular [4+2]
Diels–Alder cyclo-additions depends upon the nature of
the metal and its ancillary ligands. [1] The diastereo-se-
lectivity is generally thermodynamically controlled and
is a primary function of steric effects within the metal’s
coordination sphere. The [(h5-C5H5)Ru(DMPP)3−n(di-
eneophile)n]PF6 system [1d] promotes these reactions with
the widest variety of dieneophiles yet found and in some
cases with quite high diastereoselectivity.
2.2. Synthesis
All of the [(h6-arene)Ru(DMPP)(dieneophile)Cl]PF6
complexes were prepared in the following manner. To a
solution containing 1.0 mmol of the appropriate (h6-
arene)Ru (DMPP)Cl2 complex in 25 ml of CH2Cl2 was
added 1.0 mmol of solid NaPF6. The reaction vessel was
purged with nitrogen for 30 min. Then 1.1 mmol of the
appropriate dieneophilic ligand was added via syringe and
thereactionmixturewasstirredundernitrogenatambient
temperature for 48 h. The initially deep red solution
became orange or yellow, depending upon the ligand, as
the reaction proceeded. The solution was gravity filtered
to remove NaCl and the filtrate was taken to dryness on
a rotary evaporator. The resulting solid or oil was
dissolved in a minimum amount of CH2Cl2, and after
filtering the solution, ether was added to the filtrate to
induce crystallization. The yellow or orange microcrystals
thatresultedwereisolatedbyfiltration, washedwithether,
and dried under vacuum at ambient temperature. The
yields, colors, meltingpoints, andanalyticaldataaregiven
in Table 1. 31P{1H}-NMR and IR data are given in Table
Ruthenium(II) complexes of the type [(h6-arene)-
Ru(AB)X]+X−, where AB is an optically pure bidentate
ligand and X is a halide, are efficient catalysts for the
asymmetric transfer hydro-genation of ketones [6], alke-
nes [7], and imines [8]. The potential catalytic activity of
new species of this type containing conformationally rigid
asymmetric bidentate ligands, together with our desire to
gain further insight regarding those factors that determine
the scope and diastereoselectivity of the metal promoted
intramolecular [4+2] Diels–Alder cycloaddition reac-
tions of phospholes prompted us to investigate the
reactions of the (h6-arene)Ru(DMPP)Cl2 complexes with
selected dieneophilic ligands.
2. Experimental
1
2 and H- and 13C{1H}-NMR data follow.
2.1. Reagents and physical measurements
All chemicals were reagent grade and were used as
received from commercial sources (Aldrich, Fischer,
Organometallics, Alpha/AESAR) or synthesized as de-
scribed below. DMPP [9] and the (h6-arene)Ru(R3P)Cl2
[10] complexes were synthesized by literature methods.
Solvents were dried by standard procedures and stored
2.2.1. [(p6-C6Me6)Ru(DMPP)(DPVP)Cl]PF6 (1)
1H-NMR (499.8 MHz, CD3NO2, 25°C) l 8.0–7.3 (m,
,
over Linde type 4 A molecular sieves. All reactions
3
4
involving phosphines were conducted under a purified
nitrogen atmosphere by standard Schlenk techniques.
Elemental analyses were performed by Galbraith Labo-
ratories, Knoxville, TN. Melting points were determined
15H, Ph), 3.97 (dd, J(H1H2)=3.0 Hz, J(H1H5)=2.0
Hz, 1H, H1), 3.33 (ddddd, 3J(PH)=41.0 Hz, 3J(H2H4)=
9.0 Hz, 2J(PH)=6.5 Hz, 3J(H1H2)=3.0 Hz, 3J(H2H3)=
0.5 Hz, 1H, H2), 3.06 (dd, 3J(H3H5)=4.0 Hz,

Table 1
Percent yields, colors, melting points, and analytical data for compounds 1–20
Arene
Dieneophile
%yield
Color
m.p. (°C)
%C (Calc.)
%C (Found)
%H (Calc.)
%H (Found)
%Cl (Calc.)
%Cl (Found)
(1) C6Me6
(2) C6Me6
(3a) C6Me6
(3b) C6Me6
(4) C6Me6
(5) C6Me6
(6) C6Me6
(7) p-MeC6H4CHMe2
(8) p-MeC6H4CHMe2
(9) p-MeC6H4CHMe2
(10) p-MeC6H4CHMe2
(11) p-MeC6H4CHMe2
(12) p-MeC6H4CHMe2
(13) C6H6
(14) C6H6
(15) C6H6
(16) MeC6H5
(17) MeC6H5
DPVP
PVS
58.5
54.6
72.0
72.0
62.3
71.4
56.0
57.0
58.7
68.2
42.7
59.0
53.3
50.0
57.6
76.3
60.5
41.0
68.3
65.4
70.1
Yellow
Orange
Orange
Yellow
Red
250–251
240–241
265–267
265–267
294–296
280–281
227–228
243–245
221–222
169–171
126–127
210–211
135–136
210–212
217–218
265–266
270–272
170–172
268–270
291–293
284–286
54.01
50.05
49.03
49.03
47.92
47.66
50.53
48.58
48.70
47.67
46.35
46.08
49.14
50.59
45.67
46.00
51.22
49.05
46.84
56.65
53.49
54.06
49.86
48.94
48.87
47.79
47.58
50.41
48.39
48.56
47.60
46.27
45.93
48.75
50.38
45.52
45.84
51.09
48.75
46.76
56.39
53.39
5.21
5.08
4.98
4.98
5.27
5.47
5.16
4.99
4.73
4.63
4.90
5.26
4.80
4.21
3.95
3.98
4.39
4.16
4.20
5.56
5.06
5.14
5.12
4.73
4.85
5.16
5.39
5.02
4.82
4.61
4.58
4.69
5.18
4.67
4.14
3.86
3.87
4.50
4.02
4.09
5.47
4.98
4.19
4.62
4.52
4.52
5.05
4.85
4.81
4.78
4.79
4.69
5.26
5.04
5.00
4.67
5.18
5.43
4.58
5.08
5.32
4.29
4.27
4.10
4.39
4.37
4.46
4.93
4.68
4.63
4.64
4.58
4.61
5.12
4.86
4.83
4.51
5.09
5.25
4.62
4.94
5.17
4.18
4.13
PVSO
PVSO
MVK
DMAA
2VP
DPVP
PVS
PVSO
MVK
DMAA
2VP
DPVP
PVS
2VP
DPVP
PVS
2VP
/
Red
Orange
Yellow
Orange
Yellow
Red
Red
Yellow
Yellow
Orange
Yellow
Yellow
Yellow
Orange
Red
613
(
(18) MeC6H5
(19) C6Me6
(20) p-MeC6H4CHMe2
ADPP
ADPP
177
Orange
199

180
K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
2
4J(H1H5)=2.0 Hz, 1H, H5), 2.27 (dddd, J(PH)=23.5
2.2.2. [(p6-C6Me6)Ru(DMPP)(PVS)Cl]PF6 (2)
Hz,
2J(H3H4)=13.5
Hz,
2J(H3H5)=4.0
Hz,
1H-NMR (499.8 MHz, CD3NO2, 25°C) l 7.92 (m,
2H, Ho, PPh), 7.59 (m, 1H, Hp, PPh), 7.46 (m, 7H, Hm,
PPh, Ho,m,p, SPh), 4.04 (apparent ddt, 3J(PH)=37.0
3J(H2H3)=0.5 Hz, 1H, H3), 1.83 (s, 3H, CH3), 1.71 (s,
18H, h6-C6Me6), 1.53 (dddd, 3J(PH)=23.5 Hz,
3J(PH)=20.0 Hz, J(H3H4)=13.5 Hz, J(H2H4)=9.0
Hz, J(H2H4)=9.5 Hz, J(H2H3)=3J(H1H2)=2.0 Hz,
2
3
3
3
Hz, 1H, H4), 1.36 (s, 3H, CH3). 13C{1H}-NMR (125.7
1H, H2), 3.75 (dd, J(H3H5)=3.0 Hz, J(H1H5)=2.0
3
4
2
2
MHz, CD3NO2, 25°C) l 140.20 (dd, J(PC)=2.6 Hz,
Hz, 1H, H5), 3.48 (apparent q, J(PH)=3J(H1H2)=
4J(PC)=1.9 Hz, C5), 134.05 (dd, 1J(PC)=41.6 Hz,
4J(H2H5)=2.0 Hz, 1H, H2), 2.31 (ddd, J(PH)=25.0
3
3J(PC)=0.6 Hz, Ci), 132.72 (d, J(PC)=7.5 Hz, Co),
Hz, J(H3H4)=14.5 Hz, J(H2H4)=9.5 Hz, 1H, H4),
2.11 (s, 18H, h6-C6Me6), 1.80 (apparent quin, 4J(PH)=
5J(HH)=1.0 Hz, 3H, CH3), 1.68 (ddd, 2J(H3H4)=14.5
Hz, 3J(H3H5)=3.0 Hz, 3J(H2H3)=2.0 Hz, 1H, H3),
1.56 (q, 5J(HH)=1.0 Hz, 3H, CH3). 13C{1H}-NMR
(125.7 MHz, CD3NO2, 25°C) l 140.60 (s, Ci, SPh),
133.52 (d, 2J(PC)=7.5 Hz, Co, PPh), 131.74 (d,
4J(PC)=2.3 Hz, Cp, PPh), 130.48 (s, C5), 129.61 (s,
C6), 129.10 (s, Cm, SPh), 128.80 (s, Co, SPh), 128.71 (s,
2
2
3
2
4
132.64 (d, J(PC)=12.4 Hz, Co), 131.49 (d, J(PC)=
4
3.5 Hz, Cp), 131.24 (d, J(PC)=2.5 Hz, Cp), 131.18 (d,
2J(PC)=12.6 Hz, Co), 131.15 (d, J(PC)=2.5 Hz, Co),
4
130.72 (dd, 2J(PC)=15.3 Hz, 3J(PC)=0.8 Hz, C6),
1
3
129.59 (d, J(PC)=50.9 Hz, Ci), 129.14 (d, J(PC)=
10.8 Hz, Cm), 129.01 (d, J(PC)=9.4 Hz, Cm), 128.73
3
1
3
(dd, J(PC)=38.3 Hz, J(PC)=1.6 Hz, Ci), 128.49 (d,
3J(PC)=8.2 Hz, Cm), 106.34 (apparent t, 2J(PC)=
1
3
2J(P%C)=2.1 Hz, h6-C6Me6), 58.05 (dd, J(PC)=34.1
Cp, SPh), 128.31 (d, J(PC)=9.7 Hz, Cm, PPh), 126.53
Hz, 3J(PC)=12.7 Hz, C1), 50.12 (dd, 1J(PC)=35.5
(d, J(PC)=41.0 Hz, Ci, PPh), 101.20 (d, J(PC)=2.0
1
2
1
1
Hz, J(PC)=0.6 Hz, C4), 34.27 (dd, J(PC)=40.0 Hz,
2J(PC)=29.0 Hz, C2), 31.17 (dd, 2J(PC)=10.2 Hz,
2J(PC)=1.5 Hz, C3), 14.66 (s, h6-C6Me6), 13.97 (ap-
parent t, 3J(PC)=4J(PC)=1.8 Hz, CH3), 12.24 (d,
3J(PC)=3.3 Hz, CH3).
Hz, h6-C6Me6), 57.68 (d, J(PC)=38.1 Hz, C1), 45.43
1
2
(d, J(PC)=28.3 Hz, C4), 42.36 (d, J(PC)=32.2 Hz,
2
C2), 32.54 (d, J(PC)=20.1 Hz, C3), 14.99 (s, C6Me6),
13.41 (d, J(PC)=2.6 Hz, CH3), 12.98 (d, J(PC)=2.3
3
3
Hz, CH3).
Table 2
31P{1H}-NMR and infrared data for complexes 1–20 a
Compound l P7 (ppm)
l P2 (ppm)
2J(PP) (Hz)
l PF6 (ppm) 1J(PF) (Hz)
−
%DE
82
w(CO or SO)
(cm−1
w(PF) (cm−1
)
)
1a
1b
2a
2b
3a
3b
4
148.06
142.65
147.64
145.10
146.95
147.29
117.75
119.13
122.21
142.72
139.23
146.17
146.25
143.74
114.18
116.09
119.73
141.99
144.33
140.69
118.40
142.75
138.49
145.22
141.58
119.60
29.44
63.93
58.96
54.9
55.9
−145.07
−145.07
−145.00
−145.00
−145.00
−145.00
−145.00
−145.00
−145.00
−145.00
−145.00
−145.00
−145.00
−145.00
−145.00
−145.00
−144.99
−145.10
−145.12
−145.12
−145.00
−145.04
−145.04
−144.99
−144.99
−145.00
−144.90
−145.00
707
707
708
708
708
708
708
708
708
707
707
708
708
708
708
708
708
708
708
708
708
708
708
708
708
707
713
708
837, 556
831, 557
832, 557
55.6
50
1096
\99
\99
\99
87.8
44.9
\99
\99
\99
\99
\99
1699
1699
840, 557
837, 556
836, 557
845, 557
5
6
7a
7b
8a
8b
9
59.00
45.17
56.1
50.2
829, 556
1078
1700
1699
834, 558
836, 558
843, 558
831, 557
838, 556
845, 557
10
11
12
13
14a
14b
15
16a
16b
17a
17b
18
19
20
59.51
57.7
84.2
\99
86
843, 557
835, 557
56.50
47.29
57.3
51.6
85.8
\99
837, 557
833, 556
843, 556
835, 556
29.09
25.16
56.7
53.4
28.47
a Compounds numbered a are the major diastereomer while those numbered b are the minor diastereomer.

K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
181
2.2.3. [(p6-C6Me6)Ru(DMPP)(PVSO)Cl]PF6 (3a,b)
1H-NMR (499.8 MHz, CD3NO2, 25°C) (3a) l 8.25
1.97 (s, 18H, h6-C6Me6), 1.85 (s, 3H, CH3), 1.46 (s, 3H,
CH3). 13C{1H}-NMR (125.7 MHz, CD3NO2, 25°C) l
3
(m, 2H, Ho, SPh), 7.58–7.88 (m, 8H, Hm, p, SPh, Ho,m,p
,
231.82 (s, CꢀO), 138.89 (s, C5), 134.67 (d, J(PC)=2.0
PPh), 4.07 (dddd, 3J(PH)=37.5 Hz, 3J(H2H4)=8.5
Hz, 3J(H1H2)=2.5 Hz, 3J(H2H3)=1.0 Hz, 1H, H2),
Hz, C6), 133.25 (d, 2J(PC)=7.9 Hz, Co), 131.29 (d,
3
4J(PC)=2.5 Hz, Cp), 128.15 (d, J(PC)=9.7 Hz, Cm),
3
1
3.95 (apparent t, J(H1H2)=4J(H1H5) =2.5 Hz, 1H,
127.53 (d, J(PC)=42.4 Hz, Ci), 97.86 (d, J(PC)=2.5
4
3
2
H1), 3.10 (dd, J(H1H5)=2.5 Hz, J(H3H5)=2.0 Hz,
Hz, h6-C6Me6), 49.35 (d, J(PC)=15.7 Hz, C2), 49.22
2
3
1
1
1H, H5), 2.11 (ddd, J(H3H4) =14.0 Hz, J(H3H5)=
(d, J(PC)=30.9 Hz, C1), 47.41 (d, J(PC)=29.4 Hz,
2.0 Hz, 3J(H2H3)=1.0 Hz, 1H, H3), 1.95 (s, 18H,
C4), 34.25 (s, CH3C(O)), 30.54 (d, J(PC)=24.1 Hz,
2
h6-C6Me6), 1.86 (s, 3H, CH3), 1.40 (ddd, J(PH)=21.5
C3), 14.81 (s, h6-C6Me6), 13.14 (d, 3J(PC)=2.3 Hz,
3
2
3
3
Hz, J(H3H4)=14.0 Hz, J(H2H4)=8.5 Hz, 1H, H4),
1.38 (s, 3H, CH3). (3b) l 7.90 (m, 2H, Ho, PPh), 7.76
(m, 2H, Ho, SPh), 7.68 (m, 1H, Hp, SPh), 7.67 (m, 2H,
Hm, SPh), 7.64 (m, 1H, Hp, PPh), 7.53 (m, 2H, Hm,
PPh), 4.50 (dddd, 3J(PH)=40.0 Hz, 3J(H2H4)=8.8
Hz, 3J(H1H2)=2.0 Hz, 3J(H2H3)=1.5 Hz, 1H, H2),
3.84 (apparent dq, 3J(H3H5)=4.0 Hz, 2J(PH)=
3J(H4H5)=4J(H1H5)=2.0 Hz, 1H, H5), 3.26 (apparent
q, 2J(PH)=3J(H1H2)=4J(H1H5)=2.0 Hz, 1H, H1),
2.76 (ddd, 2J(H3H4)=15.0 Hz, 3J(H3H5)=4.0 Hz,
CH3), 12.54 (d, J(PC)=2.3 Hz, CH3).
2.2.5. [(p6-C6Me6)Ru(DMPP)(DMAA)Cl]PF6 (5)
1H-NMR (499.8 MHz, CD3NO2, 25°C) l 7.89 (m,
2H, Ho), 7.53 (m, 1H, Hp), 7.47 (m, 2H, Hm), 3.92
3
4
(apparent dt, J(H3H5)=4.0 Hz, J(H1H5)=2J(PH)=
2.0 Hz, 1H, H5), 3.27 (dddd, 3J(PH)=22.0 Hz,
3J(H2H4)=9.0 Hz, J(H2H3)=5.0 Hz, J(H1H2) =1.5
Hz, 1H, H2), 3.23 (s, 3H, NCH3), 3.19 (apparent td,
2J(PH)=3J(H1H5)=2.0 Hz, 3J(H1H2)=1.5 Hz, 1H,
H1), 3.14 (s, 3H, NCH3), 2.03 (m, 1H, H3), 1.95 (m, 1H,
H4), 1.93 (s, 18H, h6-C6Me6), 1.86 (s, 3H, CH3), 1.46 (s,
3H, CH3). 13C{1H}-NMR (125.7 MHz, CD3NO2, 25°C)
3
3
3J(H2H3)=1.5 Hz, 1H, H3), 2.29 (dddd, J(PH)=25.0
3
Hz,
2J(H3H4)=15.0
Hz,
3J(H2H4)=8.8
Hz,
3J(H4H5)=2.0 Hz, 1H, H4), 2.13 (s, 18H, h6-C6Me6),
1.86 (s, 3H, CH3), 1.59 (s, 3H, CH3). 13C{1H}-NMR
(125.7 MHz, CD3NO2, 25°C) (3a) l 140.76 (s, C5),
140.64 (s, C6), 133.88 (s, Cp, SPh), 132.98 (broad d,
2J(PC)=14.7 Hz, Co, PPh), 132.28 (broad s, Co, PPh),
2
l 181.42 (s, CꢀO), 139.11 (s, C5), 135.49 (d, J(PC)=
2
1.6 Hz, C6), 133.17 (d, J(PC)=8.2 Hz, Co), 131.03 (d,
4J(PC)=2.0 Hz, Cp), 128.28 (d, J(PC)=40.1 Hz, Ci),
1
3
128.13 (d, J(PC)=9.3 Hz, Cm), 98.89 (d, J(PC)=2.4
4
Hz, h6-C6Me6), 53.30 (d, J(PC)=31.6 Hz, C1), 46.45
1
132.05 (d, J(PC)=2.6 Hz, Cp, PPh), 129.49 (s, Cm,
1
2
SPh), 129.38 (broad s, Cm, PPh), 128.83 (broad d,
(d, J(PC)=28.4 Hz, C4), 39.78 (d, J(PC)=15.7 Hz,
C2), 38.67 (s, NCH3), 37.74 (s, NCH3), 29.29 (d,
2J(PC)=23.9 Hz, C3), 14.59 (s, h6-C6Me6), 13.14 (d,
3J(PC)=2.4 Hz, CH3), 12.56 (s, 3J(PC)=2.4 Hz,
CH3).
3J(PC)=6.2 Hz, Cm, PPh), 127.85 (s, Co, SPh), 125.20
1
(d, J(PC)=41.6 Hz, Ci, PPh), 108.17 (d, J(PC)=2.0
2
Hz, h6-C6Me6), 65.28 (d, J(PC)=34.8 Hz, C2), 52.07
1
1
(d, J(PC)=31.9 Hz, C1), 48.51 (d, J(PC)=34.3 Hz,
C4), 28.31 (d, 2J(PC)=10.6 Hz, C3), 15.22 (s, h6-
C6Me6), 13.93 (d, 3J(PC)=1.8 Hz, CH3), 12.63 (d,
3J(PC)=3.1 Hz, CH3). (3b) l 141.57 (s, C5), 139.44 (s,
C6), 133.63 (d, 2J(PC)=7.8 Hz, Co, PPh), 132.49 (s, Cp,
2.2.6. [(p6-C6Me6)Ru(DMPP)(2VP)Cl]PF6 (6)
1H-NMR (499.8 MHz, CD3NO2, 25°C) l 8.92 (dd,
4
3J(HaHb)=6.0 Hz, J(HaHc)=1.5 Hz, 1H, Ha), 8.00
4
3
(m, 2H, Ho), 7.89 (apparent td, J(HbHc)=3J(HcHd)=
SPh), 132.38 (d, J(PC)=2.4 Hz, Cp, PPh), 129.05 (s,
3
4
Cm, SPh), 128.69 (d, J(PC)=9.9 Hz, Cm, PPh), 127.92
8.0 Hz, J(HaHc)=1.5 Hz, 1H, Hc),
1
(s, Ci, SPh), 126.03 (s, Co, SPh), 124.93 (d, J(PC)=
42.6 Hz, Ci, PPh), 106.45 (d, J(PC)=1.9 Hz, h6-
C6Me6), 60.87 (d, 2J(PC)=33.7 Hz, C2), 53.79 (d,
1
1J(PC)=35.3 Hz, C1), 44.74 (d, J(PC)=30.3 Hz, C4),
2
27.80 (d, J(PC)=18.7 Hz, C3), 15.07 (s, h6-C6Me6),
3
3
13.57 (d, J(PC)=2.8 Hz, CH3), 12.78 (d, J(PC)=2.8
Hz, CH3).
7.54 (m, 1H, Hp), 7.46 (m, 2H, Hm), 7.41 (ddd,
3
4
2.2.4. [(p6-C6Me6)Ru(DMPP)(MVK)Cl]PF6 (4)
3J(HbHc)=8.0 Hz, J(HaHb)=6.0 Hz, J(HbHd)=1.5
3
4
1H-NMR (499.8 MHz, CD3NO2, 25°C) l 7.90 (m,
2H, Ho), 7.54 (m, 1H, Hp), 7.46 (m, 2H, Hm), 4.06
Hz, 1H, Hb), 7.37 (dd, J(HcHd)=8.0 Hz, J(HbHd)=
1.5 Hz, 1H, Hd), 4.00 (apparent quin, 2J(PH)=
4J(H1H5)=3J(H3H5)=3J(H4H5)=1.5 Hz, 1H, H5),
3.43 (dddd, 3J(PH)=24.5 Hz, 3J(H2H4)=10.5 Hz,
(apparent
quin,
2J(PH)=3J(H3H5)=3J(H4H5)=
3
4J(H1H5)=2.0 Hz, 1H, H5), 3.40 (dddd, J(PH)=22.5
3
Hz,
3J(H2H4)=10.0
Hz,
3J(H2H3)=4.5
Hz,
3J(H2H3)=5.0 Hz, J(H1H2)=1.5 Hz, 1H, H2), 2.65
3J(H1H2)=2.0 Hz, 1H, H2), 3.14 (apparent q,
2J(PH)=3J(H1H2)=4J(H1H5)=2.0 Hz, 1H, H1), 2.68
(s, 3H, CH3C(O)), 2.19 (m, 1H, H4), 2.02 (m, 1H, H3),
(apparent q, 2J(PH)=4J(H1H5)=3J(H1H2)=1.5 Hz,
1H, H1), 2.36 (dddd, 3J(PH)=33.0 Hz, 2J(H3H4)=
3
3
12.5 Hz, J(H2H4)=10.5 Hz, J(H4H5)=1.5 Hz, 1H,

182
K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
H4), 2.24 (dddd, 2J(H3H4)=12.5 Hz, 3J(H2H3)=5.0
Hz, 3J(H3H5)=1.5 Hz, 1H, H3), 1.95 (s, 18H, h6-
C6Me6), 1.88 (s, 3H, CH3), 1.45 (s, 3H, CH3). 13C{1H}-
NMR (125.7 MHz, CD3NO2, 25°C) l 167.62 (s, Ca),
2.2.8. [(p6-p-MeC6H4CHMe2)Ru(DMPP)(PVS)Cl]PF6
(8a,b)
1H-NMR (499.8 MHz, CD3NO2, 25°C) (8a) l 7.82
3
(m, 2H, Ho, PPh), 7.62 (d, J(HH)=8.0 Hz, 2H, Ho,
3
159.71 (d, J(PC)=6.7 Hz, Ce), 138.93 (s, Cc), 136.66
SPh), 7.56 (m, 1H, Hp, PPh), 7.46 (m, 5H, Hm, SPh,
2
3
(s, C5), 135.03 (s, C6), 133.84 (d, J(PC)=7.5 Hz, Co),
PPh, Hp, SPh), 6.48 (d, J(HH)=6.5 Hz, 1H, Cy), 6.08
4
1
3
131.01 (d, J(PC)=2.2 Hz, Cp), 128.45 (d, J(PC)=
42.0 Hz, Ci), 127.76 (d, 3J(PC)=9.3 Hz, Cm), 127.34 (s,
Cd), 123.99 (s, Cb), 100.68 (d, J(PC)=2.3 Hz, h6-
C6Me6), 49.07 (d, 1J(PC)=30.2 Hz, C1), 47.18 (d,
(dd, J(HH)=6.5 Hz, J(PH)=1.0 Hz, 1H, Cy), 5.96
3
3
(d, J(HH)=5.5 Hz, 1H, Cy), 5.65 (d, J(HH)=5.5
Hz, 1H, Cy), 4.10 (apparent ddt, 3J(PH)=38.5 Hz,
3J(H2H4)=9.0 Hz, J(H1H2)=3J(H2H3)=2.0 Hz, 1H,
3
2
4
2
1J(PC)=32.3 Hz, C4), 46.82 (d, J(PC)=17.7 Hz, C2),
H2), 3.71 (dd, J(H1H5)=1.5 Hz, J(PH)=1.0 Hz, 1H,
2
3
4
31.18 (d, J(PC)=25.9 Hz, C3), 14.95 (s, h6-C6Me6),
H5), 3.56 (apparent dt, J(H1H2)=2.0 Hz, J(H1H5)=
3
3
3
13.10 (d, J(PC)=2.8 Hz, CH3), 12.55 (d, J(PC)=2.4
2J(PH)=1.5 Hz, 1H, H1), 2.45 (sept, J(HH)=7.0 Hz,
Hz, CH3).
1H, CH), 2.38 (ddd, 3J(PH)=25.0 Hz, 2J(H3H4)=14.0
Hz, 3J(H2H4)=9.0 Hz, 1H, H4), 2.21 (s, 3H, CH3),
2
3
1.93 (dd, J(H3H4)=14.0 Hz, J(H2H3)=2.0 Hz, 1H,
H3), 1.68 (s, 3H, CH3), 1.66 (s, 3H, CH3), 1.03 (d,
3
2.2.7. [(p6-p-MeC6H4CHMe2)Ru(DMPP)(DPVP)-
Cl]PF6 (7)
3J(HH)=7.0 Hz, 3H, CH3), 0.70 (d, J(HH)=7.0 Hz,
3
3H, CH3). (8b) l 7.93 (d, J(HH)=8.0 Hz, 2H, Ho,
1H-NMR (499.8 MHz, CD3NO2, 25°C) l 8.0–7.5 (m,
SPh), 7.80 (m, 2H, Ho, PPh), 7.69 (m, 1H, Hp, PPh),
3
15H, Ph), 5.91 (dd, J(HH)=6.0 Hz, J(PH)=1.0 Hz,
7.48 (m, 4H, Hm, PPh, SPh), 7.43 (m, 1H, Hp, SPh),
3
3
3
1H. Cy), 5.62 (d, J(HH)=6.0 Hz, 1H, Cy), 5.45 (d,
6.10 (d, J(HH)=6.5 Hz, 1H, Cy), 5.94 (d, J(HH)=
3
3
3J(HH)=6.0 Hz, 1H, Cy), 5.22 (d, J(HH)=6.0 Hz,
6.5 Hz, 1H, Cy), 5.50 (d, J(HH)=6.0 Hz, 1H, Cy),
1H, Cy), 3.87 (apparent q, 4J(H1H5)=2J(PH)=
3J(H1H2)=2.0 Hz, 1H, H1), 3.56 (ddddd, 3J(PH)=
41.5 Hz, 3J(H2H4)=9.5 Hz, 2J(PH)=5.5 Hz,
5.42 (d, 3J(HH)=6.0 Hz, 1H, Cy), 3.34 (dd,
4J(H1H5)=1.5 Hz, 2J(PH)=1.0 Hz, 1H, H1), 3.24
(apparent dt, J(H3H5)=2.0 Hz, J(H1H5)=2J(PH)=
3
4
3
3J(H1H2)=2.0 Hz, J(H2H3)=0.5 Hz, 1H, H2), 3.19
1.5 Hz, 1H, H5), 2.53 (m, 3H, CH, H2, H3), 2.03 (s, 3H,
3
4
3
2
(dd, J(H3H5)=4.0 Hz, J(H1H5)=2.0 Hz, 1H, H5),
CH3), 1.82 (ddd, J(PH)=22.0 Hz, J(H3H4)=3.0 Hz,
2.40 (dddd, 2J(PH)=23.5 Hz, 2J(H3H4)=13.0 Hz,
3J(H2H4)=7.5 Hz, 1H, H4), 1.77 (s, 3H, CH3), 1.51 (s,
3
3
3J(H3H5)=4.0 Hz, J(H2H3)=0.5 Hz, 1H, H3), 2.10
3H, CH3), 1.22 (d, J(HH)=7.0 Hz, 3H, CH3), 1.08 (d,
3
(sept, J(HH)=7.0 Hz, 1H, CH), 1.94 (s, 3H, CH3),
3J(HH)=7.0 Hz, 3H, CH3). 13C{1H}-NMR (125.7
MHz, CD3NO2, 25°C) (8a) l 141.00 (s, Ci, SPh), 132.34
1.70 (s, 3H, CH3). 1.67 (dddd, 3J(PH)=22.5 Hz,
2
3
2
4
3J(PH)=19.5 Hz, J(H3H4)=13.0 Hz, J(H2H4)=9.5
(d, J(PC)=8.0 Hz, Co, PPh), 131.61 (d, J(PC)=2.5
Hz, Cp, PPh), 130.10 (s, C5), 129.16 (s, Cm, SPh), 128.94
(s, Co, SPh), 128.85 (s, C6), 128.62 (s, Cp, SPh), 128.60
(d, 1J(PC)=46.8 Hz, Ci, PPh), 128.44 (d, 3J(PC)=10.3
Hz, Cm, PPh), 113.47 (s, Cy), 102.49 (s, Cy), 96.41 (d,
J(PC)=5.4 Hz, Cy), 94.57 (d, J(PC)=5.9 Hz, Cy),
3
Hz, 1H, H4), 1.49 (s, 3H, CH3), 1.10 (d, J(HH)=7.0
Hz, 3H, CH3), 0.94 (d, 3J(HH)=7.0 Hz, CH3).
13C{1H}-NMR (125.7 MHz, CD3NO2, 25°C) l 139.05
2
3
(dd, J(PC)=2.5 Hz, J(PC)=1.0 Hz, C5), 134.81 (d,
1J(PC)=44.5 Hz, Ci), 134.52 (d, 2J(PC)=10.4 Hz, Co),
131.69 (dd, 1J(PC)=41.1 Hz, 3J(PC)=1.5 Hz, Ci),
1
88.82 (s, Cy), 85.02 (s, Cy), 55.95 (d, J(PC)=40.5 Hz,
4
4
131.42 (d, J(PC)=2.4 Hz, Cp), 131.36 (d, J(PC)=2.5
C1), 48.11 (d, 1J(PC)=28.3 Hz, C4), 40.97 (d, 2J(PC)=
2
2
Hz, Cp), 131.29 (d, J(PC)=9.1 Hz, Co), 131.00 (dd,
33.6 Hz, C2), 33.20 (d, J(PC)=19.5 Hz, C3), 30.86 (s,
2J(PC)=15.2 Hz, 4J(PC)=0.9 Hz, C6), 131.00 (d,
CH), 21.42 (s, CH3), 19.46 (s, CH3), 17.46 (s, CH3),
2
3
3
4J(PC)=2.5 Hz, Cp), 130.95 (d, J(PC)=13.2 Hz, Co),
13.51 (d, J(PC)=2.8 Hz, CH3), 13.00 (d, J(PC)=2.3
Hz, CH3). (8b) l 140.19 (s, Ci, SPh), 131.73 (d,
4J(PC)=2.5 Hz, Cp, PPh), 131.43 (s, Cm, SPh), 131.04
(d, 2J(PC)=6.8 Hz, Co, PPh), 130.53 (s, C5 or C6),
1
1
129.42 (d, J(PC)=50.4 Hz, Co), 129.42 (d, J(PC)=
50.4 Hz, Ci), 129.26 (d, J(PC)=9.8 Hz, Cm), 128.63
(d, J(PC)=10.8 Hz, Cm), 118.65 (s, Cy), 106.54 (d,
3
3
1
J(PC)=1.5 Hz, Cy), 98.21 (dd, J(PC)=3.1, 1.5 Hz,
Cy), 95.64 (dd, J(PC)=3.0, 2.0 Hz, Cy), 94.95 (dd,
J(PC)=4.9, 2.3 Hz, Cy), 91.62 (d, J(PC)=4.3 Hz,
Cy), 57.13 (dd, 1J(PC)=36.6 Hz, 2J(PC)=12.7 Hz,
130.06 (s, C5 or C6), 130.00 (d, J(PC)=44.1 Hz, Ci,
3
PPh), 129.37 (d, J(PC)=11.4 Hz, Cm, PPh), 129.37 (s,
Co, SPh), 114.57 (s, Cy), 102.62 (s, Cy), 96.12 (d,
J(PC)=5.0 Hz, Cy), 94.82 (d, J(PC)=5.5 Hz, Cy),
1
3
1
C1), 48.73 (dd, J(PC)=33.8 Hz, J(PC)=0.6 Hz, C4),
31.26 (dd, 1J(PC)=39.6 Hz, 2J(PC)=30.3 Hz, C2),
30.45 (dd, 2J(PC)=10.6 Hz, 2J(PC)=2.2 Hz, C3),
29.84 (s, CH), 21.21 (s, CH3), 20.64 (s, CH3), 16.77 (s,
CH3), 13.89 (apparent t, 3J(PC)=4J(PC)=1.9 Hz,
89.94 (s, Cy), 89.07 (s, Cy), 56.13 (d, J(PC)=34.1 Hz,
C1), 45.87 (d, 1J(PC)=30.8 Hz, C4), 43.88 (d, 2J(PC)=
2
31.5 Hz, C2), 33.05 (d, J(PC)=14.0 Hz, C3), 30.18 (s,
CH), 21.54 (s, CH3), 19.92 (s, CH3), 16.68 (s, CH3),
3
3
13.76 (d, J(PC)=1.8 Hz, CH3), 12.72 (d, J(PC)=3.5
3
CH3), 12.33 (d, J(PC)=3.5 Hz, CH3).
Hz, CH3).

K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
183
2.2.9. [(p6p-MeC6H4CHMe2)Ru(DMPP)(PVSO)Cl]PF6
(9)
Cy), 99.79 (s, Cy), 93.01 (d, J(PC)=5.7 Hz, Cy), 92.07
(d, J(PC)=4.3 Hz, Cy), 87.78 (d, J(PC)=0.9 Hz, Cy),
1
1H-NMR (499.8 MHz, CD3NO2, 25°C) l 8.38 (m,
2H, Ho, SPh), 7.88 (m, 2H, Ho, PPh), 7.76 (m, 6H,
84.72 (d, J(PC)=3.0 Hz, Cy), 50.91 (d, J(PC)=29.9
Hz, C4), 49.53 (d, 2J(PC)=16.5 Hz, C2), 48.15 (d,
1J(PC)=32.7 Hz, C1), 32.25 (s, CH3C(O)), 32.10 (d,
2J(PC)=23.5 Hz, C3), 31.80 (s, CH), 22.34 (s, CH3),
3
4
Hm, p SPh, PPh), 6.14 (dd, J(HH)=6.5 Hz, J(HH)=
3
4
1.5 Hz, 1H, Cy), 6.09 (dd, J(HH)=6.5 Hz, J(HH)=
3
4
3
1.5 Hz, 1H, Cy), 5.72 (dd, J(HH)=6.5 Hz, J(HH)
21.36 (s, CH3), 18.36 (s, CH3), 14.52 (d, J(PC)=2.5
3
4
3
=1.5 Hz, 1H, Cy), 5.59 (dd, J(HH)=6.5 Hz, J(HH)
Hz, CH3), 14.11 (d, J(PC)=2.3 Hz, CH3).
=1.5 Hz, 1H, Cy), 4.30 (dddd, 3J(PH)=38.0 Hz,
3J(H2H4)=9.5 Hz, J(H2H3)=3.1 Hz, J(H1H2)=1.0
2.2.11. [(p6-p-MeC6H4CHMe2)Ru(DMPP)(DMAA)-
Cl]PF6 (11)
3
3
Hz, 1H, H2), 4.04 (apparent td, J(PH)=4J(H1H5), 2.2
2
Hz, 3J(H1H2)=1.0 Hz, 1H, H1), 3.23 (apparent t,
2J(PH)=4J(H1H5)=2.2 Hz, 1H, H5), 2.31 (sept,
1H-NMR (499.8 MHz, acetone-d6, 25°C) l 7.70 (m,
2H, Ho), 7.30 (m, 1H, Hp), 7.24 (m, 2H, Hm), 5.78 (d,
3J(HH)=7.0 Hz, 1H, CH), 2.15 (dd, J(H3H4)=14.5
3J(HH)=6.0 Hz, 1H, Cy), 5.76 (d, J(HH)=6.0 Hz,
2
3
Hz, 3J(H2H3)=3.1 Hz, 1H, H3), 2.13 (s, 3H, CH3),
1.88 (s, 3H, CH3), 1.56 (ddd, 3J(PH)=22.5 Hz,
1H, Cy), 5.52 (d, J(HH)=5.5 Hz, 1H, Cy), 5.47 (d,
3
3J(HH)=5.5 Hz, 1H, Cy), 3.91 (dd, 3J(H3H5)=3.5
2J(H3H4)=14.5 Hz, J(H2H4)=9.5 Hz, 1H, H4), 1.52
Hz, J(PH)=1.5 Hz, 1H, H5), 3.20 (dddd, J(PH)=
20.5 Hz, 3J(H2H4)=10.0 Hz, 3J(H2H3)=3.5 Hz,
3J(H1H2)=1.5 Hz, 1H, H2), 3.11 (s, 3H, NCH3), 2.97
3
2
3
3
(s, 3H, CH3), 1.19 (d, J(HH)=7.0 Hz, 3H, CH3), 1.12
(d, J(HH)=7.0 Hz, 3H, CH3). 13C{1H}-NMR (125.7
3
2
MHz, CD3NO2, 25°C) l 140.42 (s, C5), 140.17 (s, C6),
(apparent t, J(PH)=3J(H1H2)=1.5 Hz, 1H, H1), 2.93
134.11 (s, Co, SPh), 132.35 (d, 4J(PC)=2.4 Hz, Cp,
(s, 3H, NCH3), 2.13 (apparent dq, J(H3H4)=13.0 Hz,
2
2
PPh), 131.62 (d, J(PC)=7.2 Hz, Co, PPh), 129.64 (s,
2J(H2H3)=3J(PH)=3J(H3H5)=3.5 Hz, 1H, H3), 2.05
1
3
3
Cm, SPh), 129.57 (d, J(PC)=20.9 Hz, Ci, PPh), 129.57
(sept, J(HH)=7.0 Hz, 1H, CH), 1.84 (ddd, J(PH)=
(d, 3J(PC)=10.6 Hz, Cm, PPh), 128.39 (s, Ci, SPh),
128.04 (s, Co, SPh), 120.59 (s, Cy), 110.74 (s, Cy), 98.07
(d, J(PC)=2.9 Hz, Cy), 96.48 (s, Cy), 96.29 (d,
31.5 Hz, J(H3H4)=13.0 Hz, J(H2H4)=10.0 Hz, 1H,
H4), 1.61 (s, 3H, CH3), 1.50 (s, 3H, CH3), 1.32 (s, 3H,
CH3), 0.79 (d, 3J(HH)=7.0 Hz, 3H, CH3), 0.61 (d,
3J(HH)=7.0 Hz, 3H, CH3). 13C{1H}-NMR (125.7
MHz, acetone-d6, 25°C) l 181.79 (s, CꢀO), 140.53 (s,
C5), 136.03 (s, C6), 132.95 (d, 2J(PC)=7.4 Hz, Co),
2
3
2
J(PC)=3.6 Hz, Cy), 91.27 (s, Cy), 63.35 (d, J(PC)=
1
35.1 Hz, C2), 52.73 (d, J(PC)=34.3 Hz, C1), 46.87 (d,
1J(PC)=32.9 Hz, C4), 30.16 (s, CH), 28.66 (d,
2J(PC)=11.1 Hz, C3), 21.32 (s, CH3), 20.36 (s, CH3),
4
1
131.97 (d, J(PC)=2.6 Hz, Cp), 130.94 (d, J(PC)=
3
3
17.48 (s, CH3), 13.90 (d, J(PC)=1.8 Hz, CH3), 12.74
45.4 Hz, Ci), 129.27 (d, J(PC)=10.1 Hz, Cm), 105.56
3
(d, J(PC)=3.5 Hz, CH3).
(s, Cy), 98.66 (s, Cy), 92.09 (d, J(PC)=5.7 Hz, Cy),
91.37 (d, J(PC)=4.4 Hz, Cy), 86.79 (s, Cy), 84.24 (d,
2.2.10. [(p6-p-MeC6H4CHMe2)Ru(DMPP)(MVK)-
Cl]PF6 (10)
J(PC)=3.1 Hz, Cy), 51.91 (d, J(PC)=33.2 Hz, C1),
1
1
2
50.16 (d, J(PC)=29.2 Hz, C4), 39.92 (d, J(PC)=16.3
1H-NMR (499.8 MHz, acetone-d6, 25°C) l 7.93 (m,
2H, Ho), 7.54 (m, 1H, Hp), 7.47 (m, 2H, Hm), 6.18 (d,
Hz, C2), 39.72 (s, NCH3), 38.51 (s, NCH3), 31.50 (s,
2
CH), 30.81 (d, J(PC)=23.4 Hz, C3), 22.32 (s, CH3),
3
3
3J(HH)=6.5 Hz, 1H, Cy), 6.12 (d, J(HH)=6.5 Hz,
21.45 (s, CH3), 18.24 (s, CH3), 14.58 (d, J(PC)=2.6
3
1H, Cy), 5.88 (m, 2H, Cy), 4.26 (apparent dq,
3J(H3H5)=3.0 Hz, 2J(PH)=3J(H4H5)=4J(H1H5)=
1.5 Hz, 1H, H5), 3.47 (dddd, 3J(PH)=23.5 Hz,
3J(H2H4)=10.5 Hz, 3J(H2H3)=4.5 Hz, 3J(H1H2)=1.5
Hz, CH3), 14.21 (d, J(PC)=2.3 Hz, CH3).
2.2.12. [(p6-p-MeC6H4CHMe2)Ru(DMPP)(2VP)Cl]PF6
(12)
2
Hz, 1H, H2), 3.17 (apparent q, J(PH)=3J(H1H2)=
1H-NMR (499.8 MHz, CD3NO2, 25°C) l 9.64 (dd,
4J(H1H5)=1.5 Hz, 1H, H1), 2.74 (s, 3H, CH3C(O)),
3J(HaHb)=6.0 Hz, J(HaHc)=1.0 Hz, 1H, Ha), 7.92
4
2
3
2.42 (apparent ddt, J(H3H4)=13.5 Hz, J(H2H3)=4.5
(apparent
td,
3J(HbHc)=3J(HcHd)=7.5
Hz,
Hz, J(H3H5)=3J(PH)=3.0 Hz, 1H, H3), 2.32 (quin,
4J(HaHc)=1.0 Hz, 1H, Hc), 7.85 (m, 2H, Ho), 7.53 (m,
3
3J(HH)=7.0 Hz, 1H, CH), 2.20 (dddd, J(PH)=32.5
1H, Hp), 7.47 (m, 2H, Hm), 7.42 (dd, J(HcHd)=7.5
3
3
Hz, 2J(H3H4)=13.5 Hz, 3J(H2H4)=10.5 Hz,
Hz, 4J(HbHd)=1.5 Hz, 1H, Hd), 7.41 (ddd,
3J(H4H5)=1.5 Hz, 1H, H4), 1.88 (s, 3H, CH3), 1.71 (m,
3J(HbHc)=7.5 Hz, J(HaHb)=6.0 Hz, J(HbHd)=1.5
3
4
3
3
4
3H, CH3), 1.53 (s, 3H, CH3), 0.99 (d, J(HH)=7.0 Hz,
Hz, 1H, Hb), 6.20 (dd, J(HH)=6.5 Hz, J(HH)=1.0
3H, CH3), 0.84 (d, 3J(HH)=7.0 Hz, 3H, CH3).
13C{1H}-NMR (125.7 MHz, acetone-d6, 25°C) 233.05
Hz, 1H, Cy), 6.06 (d, J(HH)=6.5 Hz, 1H, Cy), 5.83
3
3
3
(d, J(HH)=5.5 Hz, 1H, Cy), 5.67 (dd, J(HH)=5.5
Hz, 4J(HH)=1.0 Hz, 1H, Cy), 4.01 (apparent q,
3J(H3H5)=3J(H4H5)=4J(H1H5)=2.0 Hz, 1H, H5),
3.51 (dddd, 3J(PH)=26.0 Hz, 3J(H2H4)=11.0 Hz,
3
(d, J(PC)=1.1 Hz, CꢀO), 140.46 (s, C5), 135.13 (d,
2J(PC)=1.5 Hz, C6), 133.14 (d, J(PC)=7.9 Hz, Co),
2
4
1
132.18 (d, J(PC)=2.5 Hz, Cp), 130.27 (d, J(PC)=
47.5 Hz, Ci), 129.29 (d, 3J(PC)=9.9 Hz, Cm), 106.34 (s,
3J(H2H3)=4.0 Hz, J(H1H2)=1.0 Hz, 1H, H2), 2.84
3

184
K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
Table 3
Crystallographic data for complexes 1–20
1
2
3a
Chemical formula
Formula weight
Crystal size (mm)
Crystal system
Space group
C38H44ClF6P3Ru·C3H6O
902.24
0.32×0.58×0.46
C
768.15
32H39ClF6P2RuS
C32H39ClF6OP2RuS
784.15
0.24×0.44×0.34
Orthorhombic
Pca2/1
21.174(3)
8.8694(5)
17.8009(11)
90
90
90
3343.0(6)
4
1.558
0.42×0.54×0.42
Orthorhombic
Pbca
18.141(3)
11.7518(14)
30.520(7)
90
90
90
6506(2)
8
1.568
Triclinic
(
P1
,
a (A)
11.4409(12)
11.5147(7)
15.5747(9)
105.535(4)
91.364(6)
92.362(6)
1973.9(3)
2
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
3
,
V (A )
Z
Dcalc (g cm−3
)
1.518
0.648
v (mm−1
)
0.783
0.766
Reflections collected
Unique reflections
8034
6898
6990
5716
7329
3267
max./min. transmission factors
Data/restraints/parameter
Goodness-of-fit
0.9122/0.8127
6898/0/478
1.028
0.8641/0.6994
5716/0/389
1.019
0.9245/0.8458
3267/1/388
1.016
R1/wR2(I\2|(I)) a
0.0358/0.0881
0.0564/0.1371
0.0465/0.0837
3b
4
5
Chemical formula
Formula weight
Crystal size (mm)
Crystal system
Space group
C32H39ClF6OP2RuS
784.15
0.08×0.48×0.38
Orthorhombic
Pbca
16.6306(15)
19.281(4)
20.7321(17)
90
C28H37ClF6OP2Ru
702.04
0.32×0.52×0.42
Triclinic
C29H40ClF6NOP2Ru
731.08
0.18×0.36×0.24
Monoclinic
P21/c
9.2334(7)
21.6872(16)
15.9245(15)
90
94.245(7)
90
(
P1
,
a (A)
10.8610(13)
10.8668(13)
13.9084(19)
93.819(10)
112.246(9)
92.962(9)
1510.7(3)
2
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
90
90
3
,
V (A )
Z
6647.8(15)
8
1.567
3176.6(5)
4
1.529
Dcalc (g cm−3
)
1.543
0.771
v (mm−1
)
0.771
0.738
Reflections collected
Unique reflections
7061
5850
6234
5317
7073
5579
max./min. transmission factors
Data/restraints/parameter
Goodness-of-fit
0.9179/0.8272
5850/0/398
1.004
0.9605/0.5593
5317/0/352
1.036
0.9929/0.9082
5579/0/371
1.048
R1/wR2(I\2|(I)) a
0.0676/0.1207
0.0601/0.1388
0.0815/0.1445
6
7
Chemical formula
Formula weight
Crystal size (mm)
Crystal system
Space group
C31H38ClF6NP2Ru
737.08
0.06×0.28×0.24
Monoclinic
P21/c
9.1122(12)
21.744(7)
15.927(3)
90
95.948(18)
90
C36H40ClF6P3Ru·0.5CH3NO2·0.5ClCH2CH2Cl
896.11
0.16×0.38×0.24
Triclinic
(
P1
,
a (A)
11.3088(13)
19.1024(16)
19.7843(16)
79.550(6)
86.821(9)
74.795(8)
4055.7(7)
4 b
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
3
,
V (A )
Z
3138.8(12)
4
1.560
Dcalc (g cm−3
)
1.468
0.694
v (mm−1
)
0.745
Reflections collected
5427
16619

K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
185
Table 3 (Continued)
6
7
Unique reflections
4110
14251
max./min. transmission factors
Data/restraints/parameter
Goodness-of-fit
0.9674/09114
4110/0/379
1.019
0.9535/0.9036
14251/12/919
1.004
R1/wR2(I\2|(I)) a
0.0703/0.1384
0.0788/0.1524
8
9
10
Chemical formula
Formula weight
Crystal size (mm)
Crystal system
Space group
C30H35ClF6P2RuS
740.10
0.16×0.36×0.36
Monoclinic
P21/c
10.5288(17)
17.834(3)
16.828(3)
90
98.263(17)
90
C30H35ClF6OP2RuS·0.5H2O
764.10
0.18×0.42×0.28
Triclinic
C26H33ClF6OP2Ru
673.98
0.22×0.44×0.38
Monoclinic
P21/n
11.3782(12)
11.1224(15)
22.628(3)
90
94.219(9)
90
(
P1
,
a (A)
10.9698(13)
12.4647(12)
12.6210(10)
84.908(7)
74.074(9)
82.634(8)
1643.2(3)
2
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
3
,
V (A )
Z
3127.1(10)
4
1.572
2855.8(6)
4
1.568
Dcalc (g cm−3
)
1.544
0.778
v (mm−1
)
0.812
0.812
Reflections collected
Unique reflections
6923
5511
6751
5759
6496
5026
max./min. transmission factors
Data/restraints/parameter
Goodness-of-fit
0.9553/0.8161
5511/0/370
1.006
0.9685/0.8939
5410/0/389
1.025
0.9302/0.8758
5026/0/334
1.016
R1/wR2(I\2|(I)) a
0.0771/0.1319
0.0408/0.0907
0.0589/0.1128
11
12
13
Chemical formula
Formula weight
Crystal size (mm)
Crystal system
Space group
C27H36ClF6NOP2Ru
703.03
0.14×0.44×0.38
Triclinic
C29H34ClF6NP2Ru·0.5C3H6O
738.07
C32H32ClF6P3Ru
760.01
0.03×0.54×0.20
Monoclinic
P21/c
12.765(3)
12.0998(9)
21.354(4)
90
106.658(14)
90
0.44×0.38×0.22
Orthorhombic
Pbcn
23.799(4)
14.707(2)
20.662(4)
90
90
90
7232(2)
8
1.356
(
P1
,
a (A)
10.813(3)
11.219(3)
14.517(6)
112.31(3)
105.97(2)
93.72(2)
1537.8(8)
2
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
3
,
V (A )
Z
3159.8(9)
4
1.598
Dcalc (g cm−3
)
1.518
0.759
v (mm−1
)
0.648
0.791
Reflections collected
Unique reflections
6067
5200
7689
6361
7039
5573
max./min. transmission factors
Data/restraints/parameter
Goodness-of-fit
0.9398/0.7410
5200/0/352
1.081
0.917/0.801
6361/0/398
1.005
0.9189/0.8162
5573/0/388
1.004
R1/wR2(I\2|(I)) a
0.0965/0.2445
0.0844/0.1949
0.0750/0.1141
14
16
17
Chemical formula
Formula weight
Crystal size (mm)
Crystal system
Space group
C26H27ClF6P2RuS
684.00
0.34×0.58×0.42
Monoclinic
P21/c
C33H34ClF6P3Ru
774.03
0.09×0.54×0.46
Monoclinic
P21/c
C27H29ClF6P2RuS
698.02
0.20×0.38×0.24
Monoclinic
P21/c
,
a (A)
11.292(3)
10.3131(15)
24.586(5)
90
91.356(14)
90
12.8105(9)
12.1936(9)
21.6418(14)
90
106.491(5)
90
10.9290(9)
10.4534(5)
25.4614(18)
90
90.368(7)
90
,
b (A)
,
c (A)
h (°)
i (°)
k (°)

186
K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
Table 3 (Continued)
14
16
17
3
,
V (A )
Z
2862.3(11)
4
1.587
3241.5(4)
4
1.586
2908.8(3)
4
1.594
Dcalc (g cm−3
)
v (mm−1
)
0.880
0.772
0.867
Reflections collected
Unique reflections
6556
5025
7206
5709
6680
5103
max./min. transmission factors
Data/restraints/parameter
Goodness-of-fit
0.9406/0.7743
5025/0/335
1.032
0.9925/0.8296
5709/0/398
1.024
0.8911/0.8729
5103/0/343
1.017
R1/wR2(I\2|(I)) a
0.0387/0.0965
0.0518/0.1024
0.0722/0.1449
18
19
20
Chemical formula
Formula weight
Crystal size (mm)
Crystal system
Space group
C26H28ClF6NP2Ru
666.95
0.18×0.40×0.32
Monoclinic
P21/n
7.2033(8)
18.0238(17)
21.062(3)
90
97.991(12)
90
C39H46ClF6P3Ru·CH2Cl2
943.11
0.12×0.48×0.18
C37H42ClF6P3Ru
830.14
0.28×0.65×0.42
Orthorhombic
P212121
14.0082(17)
15.6153(19)
16.444(2)
90
90
90
3597.0(8)
4
1.533
Triclinic
(
P1
,
a (A)
10.4121(16)
11.1175(14)
18.768(3)
98.821(10)
99.395(13)
97.072(13)
2093.5(5)
2
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
3
,
V (A )
Z
2708.0(5)
4
1.636
Dcalc (g cm−3
)
1.496
0.736
v (mm−1
)
0.854
0.702
Reflections collected
Unique reflections
6406
4769
8682
7363
4443
4228
Max/min transmission
Data/restraints/parameter
Goodness-of-fit
0.9670/0.8732
4769/0/334
1.038
0.9644/09384
7363/0/478
1.033
0.8867/07296
4228/0/434
1.004
R1/wR2(I\2|(I)) a
0.0601/01315
0.0551/0.1330
0.0273/0.0654
a R1=ꢀꢁꢁFoꢁ−ꢁFcꢁ/ꢀꢁFoꢁ; wR2={ꢀ[w(F2o−Fc2)2]/ꢀ[w(Fo)2]2}0.5
.
b Two inequivalent cations in the asymmetric unit.
(apparent t, 3J(H1H2)=4J(H1H5)=2.0 Hz, 1H, H1),
2.2.13. [(p6-C6H6)Ru(DMPP)(DPVP)Cl]PF6 (13)
2
3
2.50 (apparent ddt, J(H3H4)=13.0 Hz, J(H2H3)=4.0
1H-NMR (499.8 MHz, CD3NO2, 25°C) l 7.50–8.00
(m, 15H, Ph), 5.65 (s, 6H, h6-C6H6), 3.93 (apparent dt,
4J(H1H5)=2.5 Hz, 2J(PH)=3J(H1H2)=1.5 Hz, 1H,
H1), 3.53 (apparent dddt, 3J(PH)=40.5 Hz,
3J(H2H4)=9.5 Hz, 2J(PH)=7.5 Hz, 3J(H1H2)=
3
Hz, J(PH)=3J(H3H5)=2.0 Hz, 1H, H3), 2.38 (dddd,
3J(PH)=32.0 Hz, 2J(H3H4)=13.0 Hz, 3J(H2H4)=
11.0 Hz, 3J(H4H5)=2.0 Hz, 1H, H4), 2.30 (sept,
3J(HH)=7.0 Hz, 1H, CH), 1.75 (s, 3H, CH3), 1.74 (s,
3
3
3H, CH3), 1.56 (s, 3H, CH3), 1.02 (d, J(HH)=7.0 Hz,
3J(H2H3)=2.5 Hz, 1H, H2), 3.27 (ddd, J(H3H5)=3.5
3
3H, CH3), 0.52 (d, J(HH)=7.0 Hz, CH3). 13C{1H}-
Hz, 4J(H1H5)=1.5 Hz, 3J(H4H5)=0.5 Hz, 1H, H5),
2.41 (dddd, 3J(PH)=23.5 Hz, 2J(H3H4)=13.0 Hz,
3J(H3H5)=3.5 Hz, 3J(H2H3)=2.5 Hz, 1H, H3), 1.88 (s,
NMR (125.7 MHz, CD3NO2, 25°C) l 166.94 (d,
3J(PC)=1.3 Hz, Ce), 161.85 (s, Ca), 139.16 (s, Cc),
2
3
3
137.75 (s, C5), 134.34 (d, J(PC)=0.6 Hz, C6), 131.91
3H, CH3), 1.73 (ddddd, J(PH)=23.0 Hz, J(PH)=
21.0 Hz, 2J(H3H4)=13.0 Hz, 3J(H2H4) =9.5 Hz,
3J(H4H5)=0.5 Hz, 1H, H4), 1.59 (s, 3H, CH3).
13C{1H}-NMR (125.7 MHz, CD3NO2, 25°C) l 138.95
2
4
(d, J(PC)=7.7 Hz, Co), 130.98 (d, J(PC)=2.3 Hz,
Cp), 130.68 (d, 1J(PC)=47.5 Hz, Ci), 128.21 (d,
3J(PC)=10.1 Hz, Cm), 127.95 (s, Cd), 123.81 (s, Cb),
107.27 (s, Cy), 98.47 (s, Cy), 98.07 (d, J(PC)=5.5 Hz,
Cy), 95.98 (d, J(PC)=5.5 Hz, Cy), 88.56 (s, Cy), 85.41
(s, Cy), 50.10 (d, 1J(PC)=32.9 Hz, C4), 47.44 (d,
2
3
(dd, J(PC)=2.4 Hz, J(PC)=1.1 Hz, C5), 135.07 (d,
1J(PC)=45.5 Hz, Ci), 134.77 (d, J(PC)=9.8 Hz, Co),
2
131.90 (dd, 1J(PC)=42.9 Hz, 3J(PC)=1.3 Hz, Ci),
2
4
4
1J(PC)=31.7 Hz, C1), 45.90 (d, J(PC)=19.4 Hz, C2),
131.57 (d, J(PC)=2.6 Hz, Cp), 131.46 (d, J(PC)=2.4
Hz, Cp), 131.34 (dd, 2J(PC)=15.8 Hz, 3J(PC)=1.3
Hz, C6), 131.04 (d, 4J(PC)=2.8 Hz, Cp), 130.96 (d,
2
31.91 (d, J(PC)=24.5 Hz, C3), 30.75 (s, CH), 21.89 (s,
CH3), 19.02 (s, CH3), 17.12 (s, CH3), 13.13 (d,
3J(PC)=2.9 Hz, CH3), 12.82 (d, 3J(PC)=2.5 Hz,
CH3).
2J(PC)=9.0 Hz, Co), 129.18 (d, J(PC)=9.9 Hz, Cm),
3
3
3
129.10 (bd, J(PC)=9.2 Hz, Cm), 128.74 (d, J(PC)=

Table 4
Bond lengths (A) and bond angles (°) For complexes 1–20
,
Compound RuꢁP1
RuꢁP2
RuꢁE
RuꢁCl
RuꢁC, (ave.)
P1ꢁRuꢁP2,
P1ꢁRuꢁE
P1ꢁRuꢁCl P2ꢁRuꢁCl,
EꢁRuꢁCl
Diastereomer
ꢀÚ’s
Arene, PꢁEꢁCl, dihedral angle
/
(1)
(2)
(3a)
(3b)
(4)
(5)
(6)
(7)
(8)
2.2964(9)
2.3407(9)
2.376(2)
2.297(2)
2.297(2)
2.126(4)
2.120(7)
2.178(9)
2.332(2)
2.379(3)
2.2932(10)
2.130(4)
2.112(8)
2.142(9)
2.317(3)
2.386(1)
2.317(2)
2.386(2)
2.150(6)
2.365(2)
2.357(1)
2.4001(9)
2.408(2)
2.403(3)
2.376(2)
2.405(2)
2.400(3)
2.394(3)
2.389(3)
2.392(3)
2.3994(11)
2.388(2)
2.391(4)
2.387(3)
2.386(2)
2.378(1)
2.3876(14)
2.378(2)
2.411(2)
2.403(2)
2.402(1)
2.289(4)
2.247(6)
2.281(10)
2.270(9)
2.227(7)
2.208(12)
2.257(12)
2.266(10)
2.240(10)
2.271(4)
2.207(7)
2.205(13)
2.234(12)
2.255(10)
2.221(5)
2.256(7)
2.229(10)
2.238(8)
2.297(6)
2.268(5)
79.84(3)
82.10(6)
79.73(8)
81.68(8)
87.93(12)
86.8(2)
88.30(3)
79.75(9)
80.50(10)
79.68(4)
87.43(13)
87.5(2)
86.99(3)
85.94(6)
87.78(9)
83.33(8)
85.54(6)
84.24(10)
86.19(11)
88.01(9)
87.52(10)
86.47(4)
82.79(1)
84.09(14)
83.45(11)
88.56(9)
82.58(4)
88.12(6)
82.61(8)
84.70(6)
82.41(5)
85.37(4)
89.44(3)
89.55(6)
97.71(9)
89.03(8)
82.76(13)
83.60(3)
82.50(3)
89.95(9)
95.67(9)
95.17(4)
83.31(14)
84.0(3)
B
A
B
A
A
A
A
B
B
B
A
A
A
B
A
B
A
A
256.27 5.6
257.59 2.2
265.22 7.2
254.04 3.3
256.23 5.1
254.64 6.7
256.99 1.4
257.71 2.9
263.69 1.3
261.32 1.7
253.53 4.1
255.59 5.5
254.85 2.7
259.42 1.4
255.61 0.5
259.54 2.0
256.11 0.2
257.37 4.3
263.06 3.9
266.63 0.9
2.300(2)
2.315(2)
2.299(2)
2.305(2)
2.310(3)
2.297(3)
2.307(3)
2.284(3)
2.2914(11)
2.284(2)
2.299(3)
2.281(3)
2.282(3)
2.284(1)
2.290(2)
2.291(2)
2.276(2)
2.333(2)
2.328(1)
(9)
(10)
(11)
(12)
(13)
(14)
(16)
(17)
(18)
(19)
(20)
88.2(2)
83.2(3)
613
80.34(9)
82.06(4)
80.15(6)
81.97(9)
89.30(16)
93.00(5)
92.89(4)
90.52(9)
90.97(4)
91.27(6)
91.53(8)
83.37(16)
87.65(5)
88.37(4)
(
177
199

188
K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
1
10.7 Hz, Cm), 128.24 (d, J(PC)=51.7 Hz, Ci), 95.62 (t,
1
J(PC)=2.3 Hz, h6-C6H6), 57.44 (dd, J(PC)=37.3 Hz,
2J(PC)=12.6 Hz, C1), 47.65 (dd, 1J(PC)=33.7 Hz,
3J(PC)=1.8 Hz, C4), 31.08 (dd, 1J(PC)=39.2 Hz,
2J(PC)=30.7 Hz, C2), 30.23 (dd, 2J(PC)=11.2 Hz,
2J(PC)=2.1 Hz, C3), 13.84 (apparent t, 3J(PC)=
4J(PC)=2.1 Hz, CH3), 12.37 (d, 3J(PC)=3.6 Hz,
CH3).
2.2.14. [(p6-C6H6)Ru(DMPP)(PVS)Cl]PF6 (14)
1H-NMR (499.8 MHz, CD3NO2, 25°C) l 7.81 (m,
2H, Ho, PPh), 7.63 (m, 2H, Ho, SPh), 7.58 (m, 1H, Hp,
PPh), 7.48 (m, 4H, Hm, SPh, PPh), 7.43 (m, 1H, Hp,
SPh), 6.15 (d, J(PH)=0.5 Hz, 6H, h6-C6H6), 4.08
(apparent ddt, 3J(PH)=38.5 Hz, 3J(H2H4)=9.2 Hz,
3J(H1H2)=3J(H2H3)=2.0 Hz, 1H, H2), 3.71 (apparent
3
3
dq, J(H3H5)=3.5 Hz, J(H4H5)=2J(PH)=4J(H1H5)
=2.0 Hz, 1H, H5), 3.56 (apparent q, 2J(PH)=
3J(H1H2)=4J(H1H5)=2.0 Hz, 1H, H1), 2.39 (dddd,
3J(PH)=25.0 Hz, J(H3H4)=14.0 Hz, J(H2H4)=9.2
Hz, 3J(H4H5)=2.0 Hz, 1H, H4), 2.03 (ddd, 2J(H3H4)=
14.0 Hz, 3J(H3H5)=3.5 Hz, 3J(H2H3)=2.0 Hz, 1H,
H3), 1.69 (s, 3H, CH3), 1.66 (s, 3H, CH3). 13C{1H}-
2
3
Fig. 2. Two perspectives of the structural drawing of the cation of 2
(hydrogen atoms omitted) showing the atom numbering scheme (40
and 10% probability ellipsoids).
NMR (125.7 MHz, CD3NO2, 25°C) l 140.77 (s, C5),
132.26 (d, 2J(PC)=8.2 Hz, Co, PPh), 131.62 (d,
4J(PC)=2.0 Hz, Cp, PPh), 129.92 (s, C6), 129.15 (s, Cm,
1
SPh), 129.09 (s, Co, SPh), 128.59 (d, J(PC)=47.8 Hz,
3
Ci, PPh), 128.58 (s, Cp, SPh), 128.49 (d, J(PC)=10.4
Hz, Cm, PPh), 128.29 (s, Ci, SPh), 91.56 (d, J(PC)=2.4
Hz, h6-C6H6), 55.51 (d, 1J(PC)=41.0 Hz, C1), 48.74 (d,
1
1J(PC)=28.3 Hz, C4), 40.64 (d, J(PC)=33.6 Hz, C2),
2
3
33.27 (d, J(PC)=19.2 Hz, C3), 13.47 (d, J(PC)=3.0
3
Hz, CH3), 12.92 (d, J(PC)=2.6 Hz, CH3).
2.2.15. [(p6-C6H6)Ru(DMPP)(2VP)Cl]PF6 (15)
1H-NMR (499.8 MHz, CD3NO2, 25°C) l 9.67 (dd,
4
3J(HaHb)=6.0 Hz, J(HaHc)=1.5 Hz, 1H, Ha), 7.92
3
4
(apparent td, J(HcHd)=3J(HbHc)=7.5 Hz, J(HaHc)
Fig. 1. Two perspectives of the structural drawing of the cation of 1
(hydrogen atoms omitted) showing the atom numbering scheme (40
and 10% probability ellipsoids).
=1.5 Hz, 1H, Hc), 7.86 (m, 2H, Ho, PPh), 7.55 (m, 1H,
Hp, PPh), 7.48 (m, 2H, Hm, PPh), 7.41 (dd, J(HcHd)=
3

K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
189
7.5 Hz, 4J(HbHd)=1.5 Hz, 1H, Hd), 7.37 (ddd,
3
4
3J(HbHc)=7.5 Hz, J(HaHb)=6.0 Hz, J(HbHd)=1.5
Hz, 1H, Hb), 5.96 (d, J(PH)=1.0 Hz, 6H, h6-C6H6),
4.00 (apparent quin, J(PH)=3J(H3H5)=3J(H4H5)=
2
4J(H1H5)=1.5 Hz, 1H, H5), 3.50 (dddd, J(PH)=24.5
3
Hz,
3J(H2H4)=11.0
Hz,
3J(H2H3)=4.0
Hz,
3J(H1H2)=1.5 Hz, 1H, H2), 2.86 (apparent t,
3J(H1H2)=4J(H1H5)=1.5 Hz, 1H, H1), 2.60 (apparent
2
3
3
ddt, J(H3H4)=13.0 Hz, J(H2H3)=4.0 Hz, J(PH)=
2.0 Hz, 1H, H3), 2.35 (dddd, 3J(PH)=32.5 Hz,
2J(H3H4)=13.0 Hz, J(H2H4)=11.0 Hz, J(H4H5)=
1.5 Hz, 1H, H4), 1.74 (apparent quin, 4J(PH)=
5J(HH)=1.0 Hz, 3H, CH3), 1.60 (apparent quin,
4J(PH)=5J(HH)=1.0 Hz, 3H, CH3). 13C{1H}-NMR
(125.7 MHz, CD3NO2, 25°C) l 167.06 (s, Ca), 161.18
3
3
3
(d, J(PC)=26.4 Hz, Ce), 139.32 (s, Cc), 137.52 (s, C5),
134.40 (s, C6), 131.86 (d, J(PC)=8.0 Hz, Co), 131.13
(d, J(PC)=2.5 Hz, Cp), 130.74 (d, J(PC)=48.0 Hz,
Ci), 128.35 (d, J(PC)=10.2 Hz, Cm), 127.92 (s, Cd),
2
4
1
Fig. 4. Structural drawing of the cation of 4 (hydrogen atoms
omitted) showing the atom numbering scheme (40% probability ellip-
soids).
3
Fig. 5. Structural drawing of the cation of 5 (hydrogen atoms
omitted) showing the atom numbering scheme (40% probability ellip-
soids).
123.69 (s, Cb), 91.19 (d, J(PC)=2.5 Hz, h6-C6H6),
1
1
51.07 (d, J(PC)=33.3 Hz, C4), 47.38 (d, J(PC)=33.3
Hz, C1), 45.84 (d, 2J(PC)=19.7 Hz, C2), 30.02 (d,
2J(PC)=25.0 Hz, C3), 13.03 (d, 3J(PC)=3.1 Hz, CH3),
3
12.74 (d, J(PC)=2.4 Hz, CH3).
2.2.16. [(p6-MeC6H5)Ru(DMPP)(DPVP)Cl]PF6 (16)
1H-NMR (499.8 MHz, CD3NO2, 25°C) l 7.47–7.95
3
(m, 15H, Ph), 6.31 (d, J(HH)=6.0 Hz, 1H, tol), 5.41
(td, 3J(HH)=6.0 Hz, J(PH)=2.5 Hz, 1H, tol), 5.38 (d,
3
3J(HH)=6.0 Hz, 1H, tol), 5.15 (td, J(HH)=6.0 Hz,
3
J(PH)=2.5 Hz, 1H, tol), 4.54 (t, J(HH)=6.0 Hz, 1H,
tol), 3.92 (apparent td, 3J(H1H2)=2J(PH)=1.5 Hz,
4J(H1H5)=0.6 Hz, 1H, H1), 3.51 (apparent dddt,
3J(PH)=41.5 Hz, 2J(PH)=9.5 Hz, 3J(H2H4)=8.3 Hz,
Fig. 3. Structural drawings of the cations of 3a (top) and 3b (bottom),
(hydrogen atoms omitted) showing the atom numbering scheme (40%
probability ellipsoids).

190
K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
3
3J(H2H3)=1.5 Hz, J(H1H2)=1.5 Hz, 1H, H2), 3.26
(apparent ddt, 3J(H3H5)=3.5 Hz, 2J(PH)=2.0 Hz,
4J(H1H5)=3J(H4H5)=0.6 Hz, 1H, H5), 2.45 (dddd,
3J(PH)=23.5 Hz, 2J(H3H4)=13.0 Hz, 3J(H3H5)=
3
3.5Hz, J(H2H3)=1.5 Hz, 1H, H3), 2.22 (s, 3H, CH3),
1.88 (s, 3H, CH3), 1.72 (ddddd, 3J(PH)=23.5 Hz,
2
3
3J(PH)=21.5 Hz, J(H3H4)=13.0 Hz, J(H2H4)=8.3
Hz, 3J(H4H5)=0.6 Hz, 1H, H4), 1.53 (s, 3H, CH3).
13C{1H}-NMR (125.7 MHz, CD3NO2, 25°C) l 138.97
2
3
(dd, J(PC)=2.5 Hz, J(PC)=1.3 Hz, C5), 135.12 (d,
1J(PC)=45.4 Hz, Ci), 134.66 (d, 2J(PC)=10.2 Hz, Co),
132.19 (dd, 1J(PC)=42.9 Hz, 3J(PC)=1.4 Hz, Ci),
4
4
131.50 (d, J(PC)=2.5 Hz, Cp), 131.38 (d, J(PC)=2.4
Hz, Cp), 131.21 (dd, 2J(PC)=16.8 Hz, 3J(PC)=1.1
Fig. 8. Structural drawing of the cation of 8 (hydrogen atoms
omitted) showing the atom numbering scheme (40% probability ellip-
soids).
Fig. 6. Structural drawing of the cation of 6 (hydrogen atoms
omitted) showing the atom numbering scheme (40% probability ellip-
soids).
Fig. 9. Structural drawing of the cation of 9 (hydrogen atoms
omitted) showing the atom numbering scheme (40% probability ellip-
soids).
Hz, C6), 130.97 (d, 4J(PC)=2.9 Hz, Cp), 130.97 (d,
2
2J(PC)=9.1 Hz, Co), 130.82 (bd, J(PC)=9.1 Hz, Co),
3
3
129.16 (d, J(PC)=9.9 Hz, Cm), 129.10 (bd, J(PC)=
3
9.9 Hz, Cm), 128.70 (d, J(PC)=10.9 Hz, Cm), 128.54
(d, J(PC)=51.3 Hz, Ci), 116.99 (apparent t, J(PC)=
1
2.6 Hz, tol), 99.77 (d, J(PC)=7.5 Hz, tol), 98.92 (d,
J(PC)=7.0 Hz, tol), 94.78 (d, J(PC)=2.9 Hz, tol),
92.72 (d, J(PC)=2.9 Hz, tol), 82.07 (s, tol), 57.44 (dd,
1J(PC)=37.3 Hz, 2J(PC)=12.9 Hz, C1), 47.89 (d,
1J(PC)=33.1 Hz, C4), 31.19 (dd, 1J(PC)=39.3 Hz,
2J(PC)=31.0 Hz, C2), 30.35 (dd, 2J(PC)=11.2 Hz,
3J(PC)=2.0 Hz, C3), 17.76 (s, CH3), 13.88 (apparent t,
Fig. 7. Structural drawing of the cation of 7 (hydrogen atoms
omitted) showing the atom numbering scheme (40% probability ellip-
soids).
3
3J(PC)=4J(PC)=1.9 Hz, CH3), 12.39 (d, J(PC)=3.3
Hz, CH3).

K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
191
2.2.17. [(p6-MeC6H5)Ru(DMPP)(PVS)Cl]PF6 (17)
1H-NMR (499.8 MHz, CD3NO2, 25°C) l 7.82 (m, 2H,
Ho, PPh), 7.60 (m, 2H, Ho, SPh), 7.56 (m, 1H, Hp, PPh),
7.49 (m, 4H, Hm, PPh, SPh), 7.43 (m, Hp, SPh), 6.26
(apparent t, 3J(HH)=5.7 Hz, 1H, tol), 6.21 (d,
3
3J(HH)=5.7 Hz, 1H, tol), 6.09 (apparent t, J(HH)=
5.7 Hz, 1H, tol), 5.71 (d, 3J(HH)=5.5 Hz, 1H, tol), 5.70
3
3
(dd, J(HH)=5.7 Hz, J(HH)=5.5 Hz, 1H, tol), 4.08
(apparent ddt, 3J(PH)=38.0 Hz, 3J(H2H4)=9.0 Hz,
3J(H1H2)=3J(H2H3)=2.0 Hz, 1H, H2), 3.71 (apparent
td, 3J(H1H5)=2J(PH)=2.0 Hz, 3J(H4H5)=1.0 Hz, 1H,
H5), 3.56 (apparent q, 3J(H1H2)=2J(PH)=4J(H1H5)=
Fig. 12. Structural drawing of the cation of 12 (hydrogen atoms
omitted) showing the atom numbering scheme (40% probability ellip-
soids).
2.0 Hz, 1H, H1), 2.37 (dddd, 3J(PH)=25.0 Hz,
2J(H3H4)=14.0 Hz, 3J(H2H4)=9.0 Hz, 3J(H4H5)=1.0
Hz, 1H, H4), 2.16 (s, 3H, CH3), 2.02 (dd, 2J(H3H4)=14.0
3
4
Hz, J(H2H3)=2.0 Hz, 1H, H3), 1.69 (d, J(PH)=1.0
Hz, 3H, CH3), 1.68 (d, 4J(PH)=1.0 Hz, 3H, CH3).
13C{1H}-NMR (125.7 MHz, CD3NO2, 25°C) l 140.75 (s,
2
C5), 132.26 (d, J(PC)=8.3 Hz, Co, PPh), 136.53 (d,
4J(PC)=2.6 Hz, Cp, PPh), 129.88 (s, C6), 129.13 (s, Cm,
1
SPh), 128.90 (s, Co, SPh), 128.61 (d, J(PC)=46.9 Hz,
Ci, PPh), 128.52 (s, Cp, SPh), 128.50 (s, Ci, SPh), 128.41
3
(d, J(PC)=10.3 Hz, Cm, PPh), 112.30 (d, J(PC)=2.8
Hz, tol), 92.79 (d, J(PC)=5.5 Hz, tol), 92.22 (d, J(PC)=
2.1 Hz, tol), 91.33 (s, tol), 90.29 (d, J(PC)=2.0 Hz, tol),
Fig. 10. Structural drawing of the cation of 10 (hydrogen atoms
omitted) showing the atom numbering scheme (40% probability ellip-
soids).
1
82.63 (s, tol), 55.79 (d, J(PC)=40.6 Hz, C1), 48.49 (d,
2
1J(PC)=28.4 Hz, C4), 40.76 (d, J(PC)=33.6 Hz, C2),
33.27 (d, 2J(PC)=19.2 Hz, C3), 17.92 (s, CH3), 13.49 (d,
3J(PC)=2.8 Hz, CH3), 12.94 (d, 3J(PC)=2.5 Hz, CH3).
2.2.18. [(p6-MeC6H5)Ru(DMPP)(2VP)Cl]PF6 (18)
1H-NMR (499.8 MHz, CD3NO2, 25°C) l 9.53 (dd,
4
3J(HaHb)=6.0 Hz, J(HaHc)=1.5 Hz, 1H, Ha), 7.91
(apparent
td,
3J(HbHc)=3J(HcHd)=7.5
Hz,
4J(HaHc)=1.5 Hz, 1H, Hc), 7.86 (m, 2H, Ho), 7.54 (m,
1H, Hp), 7.48 (m, 2H, Hm), 7.40 (dd, 3J(HcHd)=7.5 Hz,
4J(HbHd)=1.5 Hz, 1H, Hd), 7.37 (ddd, J(HbHc)=7.5
3
3
4
Hz, J(HaHb)=6.0 Hz, J(HbHd)=1.5 Hz, 1H, Hb),
3
6.13 (d, J(HH)=6.0 Hz, 1H, tol), 6.09 (apparent t,
3J(HH)=6.0 Hz, 1H, tol), 5.96 (apparent td, 3J(HH)=
6.0 Hz, J(PH)=1.5 Hz, 1H, tol), 5.49 (apparent t,
3J(HH)=6.0 Hz, 1H, tol), 5.15 (d, 3J(HH)=6.0 Hz, 1H,
3
2
tol), 3.97 (apparent dq, J(H3H5)=2.0 Hz, J(PH)=
3J(H4H5)=4J(H1H5)=1.5 Hz, 1H, H5), 3.50 (dddd,
3J(PH)=27.0 Hz, J(H2H4)=10.7 Hz, J(H2H3)=4.0
Hz, 3J(H1H2)=1.5 Hz, 1H, H2), 2.86 (apparent t,
3J(H1H2)=4J(H1H5)=1.5 Hz, 1H, H1), 2.57 (apparent
3
3
Fig. 11. Structural drawing of the cation of 11 (hydrogen atoms
omitted) showing the atom numbering scheme (40% probability ellip-
soids).

192
K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
Fig. 13. Structural drawing of the cation of 13 (hydrogen atoms omitted) showing the atom numbering scheme (40% probability ellipsoids).
4
ddt, 2J(H3H4)=13.0 Hz, 3J(H2H3)=4.0 Hz,
3J(H3H5)=3J(PH)=2.0 Hz, 1H, H3), 2.34 (dddd,
3J(PH)=32.5 Hz, 2J(H3H4)=13.0 Hz, 3J(H2H4)=
10.7 Hz, 3J(H4H5)=1.5 Hz, 1H, H4), 2.02 (s, 3H,
CH3), 1.75 (s, 3H, CH3), 1.59 (s, 3H, CH3). 13C{1H}-
NMR (125.7 MHz, CD3NO2, 25°C) l 167.08 (s, Ca),
133.28 (s, Cp), 132.43 (s, Cp), 132.11 (d, J(PC)=2.3
2
Hz, Cp), 132.11 (d, J(PC)=9.3 Hz, Cb%), 131.21 (d,
2J(PC)=12.1 Hz, Co), 130.74 (d, J(PC)=7.7 Hz, Co),
2
3
3
128.83 (d, J(PC)=9.6 Hz, Cm), 128.26 (d, J(PC)=
10.1 Hz, Cm), 128.15 (d, J(PC)=10.4 Hz, Cm), 126.26
(d, J(PC)=49.0 Hz, Ca), 123.36 (d, J(PC)=50.0 Hz,
3
1
1
3
3
161.67 (d, J(PC)=23.0 Hz, Ce), 139.24 (s, Cc), 137.50
Ca), 120.00 (d, J(PC)=9.7 Hz, Cg%), 105.56 (apparent
2
1
(s, C5), 134.35 (s, C6), 131.85 (d, J(PC)=7.7 Hz, Co),
t, J(PC)=2.3 Hz, h6-C6Me6), 32.91 (d, J(PC)=28.4
4
1
3
131.05 (d, J(PC)=2.1 Hz, Cp), 130.87 (d, J(PC)=
47.9 Hz, Ci), 128.29 (d, 3J(PC)=9.8 Hz, Cm), 127.83 (s,
Cd), 123.82 (s, Cb), 111.85 (d, J(PC)=3.4 Hz, tol),
96.95 (d, J(PC)=6.7 Hz, tol), 93.72 (d, J(PC)=2.1
Hz, tol), 89.79 (s, tol), 85.83 (d, J(PC)=1.8 Hz, tol),
Hz, CH2), 17.52 (d, J(PC)=12.2 Hz, CH3), 17.20 (d,
3J(PC)=12.4 Hz, CH3), 15.40 (s, h6-C6Me6).
2.2.20. [(p6-p-MeC6H4CHMe2)Ru(DMPP)(ADPP)Cl]-
PF6 (20)
1
80.45 (s, tol), 50.71 (d, J(PC)=33.2 Hz, C4), 47.54 (d,
1H-NMR (499.8 MHz, CD3NO2, 25°C) l 7.40–7.85
(m, 15H, Ph), 6.82 (dq, 2J(PH)=34.0 Hz, 4J(HH)=1.0
2
1J(PC)=31.8 Hz, C1), 45.93 (d, J(PC)=19.5 Hz, C2),
2
2
4
32.07 (d, J(PC)=24.5 Hz, C3), 17.70 (s, CH3), 13.03
Hz, 1H, Ha), 6.81 (dq, J(PH)=31.5 Hz, J(HH)=1.0
3
3
3
(d, J(PC)=2.8 Hz, CH3), 12.73 (d, J(PC)=2.4 Hz,
Hz, 1H, Ha), 5.61 (ddd, J(HH)=6.0 Hz, J(PH)=3.5
CH3).
2.2.19. [(p6-C6Me6)Ru(DMPP)(ADPP)Cl]PF6 (19)
1H-NMR (499.8 MHz, CDCl3, 25°C) l 7.14–7.64
2
(m, 15H, Ph), 6.80 (d, J(PH)=32.5 Hz, Ha), 6.62 (d,
3
2J(PH)=30.5 Hz, Ha), 5.00 (apparent dtt, J(HaHb)=
15.5 Hz, 3J(HaHc)=3J(PH)=10.0 Hz, 3J(CH2Ha)=
3
5.0 Hz, 1H, Ha), 4.79 (d, J(HaHc)=10.0 Hz, 1H, Hc),
4.44 (d, 3J(HaHb)=15.5 Hz, 1H, Hb), 3.52 (m, 2H,
CH2), 2.04 (s, 3H, CH3), 1.90 (s, 3H, CH3), 1.64 (s,
18H, h6-C6Me6). 13C{1H}-NMR (125.7 MHz, CDCl3,
25°C) l 152.86 (d, 2J(PC)=5.5 Hz, Cb), 151.59 (d,
Fig. 14. Structural drawing of the cation of 14 (hydrogen atoms
omitted) showing the atom numbering scheme (40% probability ellip-
soids).
2
2J(PC)=7.3 Hz, Cb), 135.75 (d, J(PC)=9.7 Hz, Co),

K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
193
Fig. 15. Structural drawing of the cation of 16 (hydrogen atoms omitted) showing the atom numbering scheme (40% probability ellipsoids).
Hz, 4J(HH)=1.0 Hz, 1H, Cy), 5.39 (ddd, 3J(HH)=6.0
3J(PC)=12.6 Hz, CH3), 16.45 (d, 3J(PC)=12.9 Hz,
CH3).
4
Hz, J(PH)=3.0 Hz, J(HH)=1.0 Hz, 1H, Cy), 5.33
(ddddd, 3J(HaHb)=17.0 Hz, 3J(HaHc)=10.0 Hz,
3
3
3J(HaHa%)=7.5 Hz, J(HaHa%%)=7.4 Hz, J(PH)=4.5
2.3. X-ray data collection and processing
3
4
Hz, 1H, Ha), 5.20 (dd, J(HH)=6.0 Hz, J(HH)=1.0
Hz, 1H, Cy), 5.16 (dd, J(HH)=6.0 Hz, J(HH)=1.0
3
4
Crystals of the complexes were obtained from
ClCH2CH2Cl–ether (1), acetone–ether (2, 3b, 6, 9, 10,
17, 18), CH2Cl2–ether (4, 14, 20), CH3NO2–ether (3a,
7), CH2Cl2–ether (5, 11), CH3NO2–acetone–ether (13)
or CH2Cl2–CH3OH–ether (19) mixtures, mounted on
glass fibers coated with epoxy and placed on a Siemens
P4 diffractometer. Intensity data were taken in the
v-mode at 298 K with Mo–Ka graphite monochro-
3
Hz, 1H, Cy), 4.87 (apparent ddt, J(HaHc)=10.0 Hz,
2J(HbHc)=1.5 Hz, 4J(Ha%Hc)=4J(PH)=1.0 Hz, 1H,
Hc), 4.72 (apparent dddt, 3J(HaHb)=17.0 Hz,
4J(HbHa%)=4J(HbHa%%)=4.0 Hz, J(HbHc)=4J(PH)=
2
1.0 Hz, 1H, Hb), 3.57 (ddddd, 2J(Ha%Ha%)=15.5 Hz,
2J(PH)=8.0 Hz, 3J(HaHa%)=7.5 Hz, 4J(HbHa%)=4.0
4
3
Hz, J(HcHa%)=1.0 Hz, 1H, Ha%), 2.62 (q, J(HH)=7.0
2
,
mated radiation (u=0.71073 A). Three check reflec-
Hz, 1H, CH), 2.49 (apparent dt, J(Ha%Ha%)=15.5 Hz,
2J(PH)=3J(HaHa%%)=7.4 Hz, 1H, Ha%%), 2.18 (d,
tions monitored every 100 reflections showed random
4J(HH)=1.0 Hz, 3H, CH3), 2.01 (d, J(HH)=1.0 Hz,
4
(B2%) variation during the data collections. The data
3
3H, CH3), 1.90 (s, 3H, CH3), 1.05 (d, J(HH)=7.0 Hz,
3H, CH3), 1.05 (d, 3J(HH)=7.0 Hz, 3H, CH3).
13C{1H}-NMR (125.7 MHz, CD3NO2, 25°C) l 154.86
2
2
(d, J(PC)=9.8 Hz, Cb), 152.43 (d, J(PC)=9.9 Hz,
Cb), 134.20 (dd, 1J(PC)=52.5 Hz, 2J(PC)=2.3 Hz,
Ci), 133.98 (d, 2J(PC)=9.6 Hz, Co), 133.93 (dd,
1J(PC)=46.4 Hz, 3J(PC)=1.6 Hz, Ci), 132.51 (d,
2J(PC)=8.5 Hz, Co), 131.70 (d, J(PC)=8.3 Hz, Co),
2
4
4
131.56 (d, J(PC)=2.5 Hz, Cp), 131.03 (d, J(PC)=2.5
Hz, Cp), 130.91 (d, 4J(PC)=2.6 Hz, Cp), 129.86 (d,
2J(PC)=12.2 Hz, Cb%), 128.98 (dd, J(PC)=46.6 Hz,
1
3J(PC)=1.4 Hz, Ci), 128.69 (d, J(PC)=10.2 Hz, Cm),
3
3
3
128.57 (d, J(PC)=9.9 Hz, Cm), 128.37 (d, J(PC)=
10.0 Hz, Cm), 125.52 (d, J(PC)=52.2 Hz, Ca), 124.81
1
1
(d, J(PC)=2.1 Hz, Cy), 123.45 (d, J(PC)=50.8 Hz,
Ca), 119.68 (d, 3J(PC)=9.8 Hz, Cg%), 99.56 (s, Cy),
99.10 (dd, J(PC)=3.7, 1.9 Hz, Cy), 95.07 (s, Cy), 92.41
(d, J(PC)=2.8 Hz, Cy), 88.90 (d, J(PC)=8.0 Hz, Cy),
32.07 (d, 1J(PC)=26.8 Hz, Ca%), 30.84 (s, CH), 20.85 (s,
CH3), 20.10 (s, CH3), 16.97 (s, CH3), 16.56 (d,
Fig. 16. Structural drawing of the cation of 17 (hydrogen atoms
omitted) showing the atom numbering scheme (40% probability ellip-
soids).

194
K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
inequivalent cations in the asymmetric unit. Complex
20 spontaneously resolved. The absolute configuration
was determined by refinement of the Flack parameters
[12]. Crystallographic data are given in Table 3.
3. Results
The (h6-arene)Ru(DMPP)Cl2 complexes (DMPP=
3,4-dimethyl-1-phenylphosphole) react with NaPF6 and
the dieneophilic ligands
L
[L=Ph2PCH=CH2
(DPVP), Me2NC(O)CH=CH2 (DMAA), MeC(O)CH
=CH2 (MVK), PhSCH=CH2 (PVS), PhS(O)CH=
CH2 (PVSO), and 2-vinylpyridine (2VP)] to form the
undetected [(h6-arene)Ru(DMPP)(L)Cl]PF6 intermedi-
ates that undergo spontaneous intramolecular cycload-
dition reactions as illustrated schematically in reaction
4. The fact that the mixed ligand intermediates could
not be detected suggests that the [4+2] Diels–Alder
cycloaddition reactions are faster than the ligand sub-
stitution reactions preceding them and the latter are
rate determining. This is generally the case for these
facile cycloadditions [1].
Fig. 17. Structural drawing of the cation of 18 (hydrogen atoms
omitted) showing the atom numbering scheme (40% probability ellip-
soids).
Fig. 18. Structural drawing of the cation of 19 (hydrogen atoms
omitted) showing the atom numbering scheme (40% probability ellip-
soids).
were corrected for Lorentz, polarization effects, and
absorption using an emperical model derived from az-
imuthal data collections. Scattering factors and correc-
tions for anomalous dispersions were taken from a
standard source. [11] Calculations were performed with
the Siemens SHELXTL PLUS version 5.10 software pack-
age on a personal computer. The structures were solved
by direct (3b, 6, 11, 14, 18, 20) or Patterson (1, 2, 3a, 4,
5, 7, 8, 9, 10, 12, 13, 16, 17, 19) methods. Anisotropic
thermal parameters were assigned to all non-hydrogen
atoms. Hydrogen atoms were refined at calculated posi-
tions with a riding model in which the CꢁH vector was
,
fixed at 0.96 A. Compounds 1, 7, 9, 12, and 19 crystal-
lized as acetone, CH3NO2–ClCH2CH2Cl, H2O, acetone
Fig. 19. Structural drawing of the cation of 20 (hydrogen atoms
omitted) showing the atom numbering scheme (40% probability ellip-
soids).
and CH2Cl2 solvates, respectively. For 7 there are two

K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
195
Table 5
1H Chemical shifts (ppm) for the norbornene ring protons of compounds 1–18
Compound
Diastereomer
H1
H2
H3
H4
H5
CH3(5)
CH3(6)
Arene
Dieneophile
(1)
(2)
(3a)
(3b)
(4)
(5)
(6)
(7)
B
A
B
A
A
A
A
B
B
A
B
A
A
A
B
A
A
B
3.97
3.48
3.95
3.26
3.14
3.19
2.65
3.87
3.56
3.34
4.04
3.17
2.97
2.84
3.93
3.56
2.86
3.92
3.56
2.86
3.33
4.04
4.07
4.50
3.40
3.27
3.43
3.56
4.10
2.53
4.30
3.57
3.20
3.51
3.53
4.08
3.50
3.51
4.08
3.50
2.27
1.68
2.11
2.76
2.02
2.03
2.24
2.40
1.93
2.53
2.15
2.42
2.13
2.50
2.41
2.03
2.60
2.45
2.02
2.57
1.53
2.31
1.40
2.29
2.19
1.95
2.36
1.67
2.48
1.82
1.56
2.20
1.84
2.38
1.73
2.39
2.35
1.72
2.37
2.34
3.06
3.75
3.10
3.84
4.06
3.92
4.00
3.19
3.71
3.24
3.23
4.26
3.91
4.01
3.27
3.71
4.00
3.26
3.71
3.97
1.83
1.80
1.86
1.86
1.85
1.86
1.88
1.71
1.68
1.77
1.88
1.71
1.50
1.75
1.88
1.69
1.74
1.88
1.69
1.75
1.36
1.56
1.38
1.59
1.46
1.46
1.45
1.49
1.66
1.51
1.52
1.53
1.32
1.56
1.54
1.63
1.60
1.53
1.68
1.59
HMB
HMB
HMB
HMB
HMB
HMB
HMB
Cy
Cy
Cy
Cy
Cy
Cy
Cy
Bz
Bz
Bz
Tol
Tol
Tol
DPVP
PVS
PVSO
PVSO
MVK
DMAA
2VP
DPVP
PVS
PVS
PVSO
MVK
DMAA
2VP
DPVP
PVS
2VP
DPVP
PVS
(8a)
(8b)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
A
A
2VP
The [(h6-arene)Ru(DMPP)(DPVP)Cl]PF6 Diels–
Alder adducts were also prepared by reaction 5.
with our previous report [1d] of Diels–Alder adduct
formation upon reaction of [(Cp)Ru(DMPP)2-
(CH3CN)]PF6 with diallylphenylphosphine.
The Diels–Alder reactions described herein provide
ready syntheses of chiral complexes containing confor-
mationally rigid bidentate ligands with diastereoselec-
tivities that are generally quite high and are a function
of the magnitudes of intraligand steric effects.
New compounds were characterized by 1H-, 13C{1H}-,
and 31P{1H}-NMR spectroscopy. Proton and carbon
chemical shift assignments were made by detailed anal-
The diastereomeric ratios of the common products of
reactions 4 and 5, as determined by 31P{1H}-NMR
spectroscopy of the crude products, were the same
suggesting that the diastereo-meric ratios are under
thermodynamic control. Moreover, interconversion of
the diastereomers does not occur.
No Diels–Alder cycloadducts were formed in the
reaction of (h6-MeC6H5)Ru(DMPP)Cl2 or (h6-
C6H6)Ru(DMPP)Cl2 with NaPF6 and PVSO, MVK, or
DMAA. The reactions of (h6-C6Me6) Ru(DMPP)Cl2
and (h6-p-MeC6H4CHMe2)Ru(DMPP)Cl2 with NaPF6
and allyldiphenylphosphine (ADPP) produced the
mixed ligand complexes [(h6-arene)Ru(DMPP)-
(ADPP)Cl]PF6 which did not undergo subsequent
Diels–Alder cycloadditions even after heating at 84°C
in ClCH2CH2Cl solutions for 1 week. This contrasts
ysis of H/1H decoupling, H{31P}, APT, and H/13C
HETCOR experiments and are given in the experimen-
tal section. The proton resonance line shapes were
similar to those that we have described [13] for
Ru(CO)Cl2− (DMPP) complexes of some of these lig-
ands. The NMR spectral data are characteristic of the
assigned structures.
1
1
1
4. Discussion
4.1. Diastereoselecti6ity
Because these [4+2] Diels–Alder cycloadditions all
occur intramolecularly [1] within the ruthenium coordi-

196
K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
nation sphere to form the syn-exo-7-phosphanorbornene
skeleton (illustrated below) the absolute configuration of
the C(1) and C(4) stereocenters are fixed and only those
at C(2) (the ring conjunction carbon), E, and P(7) may
vary.
In the sulfide and sulfoxide complexes, sulfur becomes
a stereocenter such that for these complexes up to four
racemic diastereomers, namely (RLSSSRu–SLRSRRu),
For the cases where ERn is ꢁPPh2, ꢁS(O)Ph or ꢁSPh,
in both enantiomers of these ligands the stereochemistry
of C(2) is the same as that of P(7). When ERn is
ꢁC(O)NMe2, ꢁC(O)CH3, or -2- pyridyl the stereochem-
istry of C(2) is opposite that of P(7) as a result of different
priorities in the CIP sequence rules [14] even though the
relative positions of the ERn moieties remain the same.
Thus, for ease of discussion, we will refer to the absolute
configuration of these chiral ligands by a single descrip-
tor, R or S. Ruthenium becomes a stereocenter in the
products and may have either R or S absolute configu-
(RLSSSRu–SLRSRRu),
(SLSSSRu–RLRSRRu),
and
(SLRSSRu–RLSSRRu) may be formed.
For simplicity, we will call the enantiomeric pairs of
diastereomers A and B, respectively and will consider the
stereochemistry at sulfur separately. The geometric struc-
tures of the major diastereomers of most of these
products were determined by X-ray crystallography
(Figs. 1–19). These structures consist of isolated cations
and anions with no short interionic contacts. Selected
bond distances and angles are given in Table 4. As can
be seen in Figs. 1, 7, 13 and 16, the major diastereomer
of each of the [(h6-arene)Ruꢁ (DMPP)(DPVP)Cl]PF6
complexes is diastereomer B. For each of these complexes
ration leading to two racemic diastereomers (RLSRu
–
SLRRu) and (SLSRu–RLRRu) for all products except those
derived from PVS and PVSO as illustrated below.
Table 6
13C{1H} chemical shifts (ppm) for the norbornene ring carbons of compounds 1–18
Compound
Diastereomer
C1
C2
C3
C4
C5
C6
CH3(5)
CH3(6)
Dieneophile
(1)
(2)
(3a)
(3b)
(4)
(5)
(6)
(7)
B
A
B
A
A
A
A
B
B
A
B
A
A
A
B
A
A
B
58.05
57.68
52.07
53.79
49.22
53.30
49.07
57.13
55.95
56.13
52.73
48.15
51.91
47.44
57.44
55.51
47.38
57.44
55.79
47.54
34.27
42.36
65.28
60.87
49.35
39.78
46.82
31.26
40.97
43.88
63.35
49.53
39.92
45.90
31.08
40.64
45.84
31.19
40.76
45.93
31.17
32.54
28.31
27.80
30.54
29.29
31.18
30.45
33.20
33.05
28.66
32.10
30.81
31.91
30.23
33.27
30.02
30.35
33.27
32.07
50.12
45.53
48.51
44.74
47.41
46.45
47.18
48.73
48.11
45.87
46.87
50.91
50.16
50.10
47.65
48.74
51.07
47.89
48.49
50.71
140.20
130.48
140.76
141.57
138.89
139.11
136.66
139.05
130.10
130.53
140.42
140.46
140.53
137.75
138.95
140.77
137.52
138.97
140.75
137.50
130.72
129.61
140.64
139.44
134.67
135.49
135.03
131.00
128.85
130.06
140.17
135.13
136.03
134.34
131.34
129.92
134.40
131.21
129.88
134.35
12.24
12.98
12.63
12.78
12.54
12.56
12.55
12.33
13.00
12.72
12.74
14.11
14.21
12.82
12.37
12.92
12.74
12.39
12.94
12.73
13.97
13.41
13.93
13.57
13.14
13.14
13.10
13.89
13.51
13.76
13.90
14.52
14.58
13.13
13.89
13.47
13.03
13.88
13.49
13.03
DPVP
PVS
PVSO
PVSO
MVK
DMAA
2VP
DPVP
PVS
PVS
PVSO
MVK
DMAA
2VP
DPVP
PVS
2VP
DPVP
PVS
(8a)
(8b)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
A
A
2VP

K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
197
Table 7
Redox characteristics of the complexes a
Compound
Complex formula
Ru(II)/Ru(III)
Reference
E1/2 V (DE, mV)
(h6-C6Me6)Ru(DMPP)Cl2
0.43 (125)
0.64 (120)
0.69 (88)
0.75 (71)
0.78 b
[1f]
[1f]
[1f]
[1f]
[1d]
[1d]
[1d]
(h6-p-MeC6H4CHMe2)Ru(DMPP)Cl2
(h6-MeC6H5)Ru(DMPP)Cl2
(h6-C6H6)Ru(DMPP)Cl2
[(Cp)Ru(DMPP)2(DPVP)]PF6 [4+2] A
[(Cp)Ru(DMPP)2(DPVP)]PF6 [4+2] B
[(Cp)Ru(DMPP)2(PVSO)]PF6 [4+2]
0.83 b
0.96 b
[(Cp)Ru(DMPP)2(PVS)]PF6 [4+2]
[(Cp)Ru(DMPP)2(2VP)]PF6 [4+2]
0.63 (95)
0.52 (53)
0.94 (101)
0.95 (240)
1.20 (256)
1.11 b
0.84 (208)
1.03 (136)
1.09 (122)
1.14 (195)
1.40 (220)
0.71 b
[1d]
[1d]
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
[(h6-C6Me6)Ru(DMPP)(DPVP)Cl]PF6 [4+2]
[(h6-C6Me6)Ru(DMPP)(PVS)Cl]PF6 [4+2]
[(h6-C6Me6)Ru(DMPP)(PVSO)Cl]PF6 [4+2]
[(h6-C6Me6)Ru(DMPP)(MVK)Cl]PF6 [4+2]
[(h6-C6Me6)Ru(DMPP)(DMAA)Cl]PF6 [4+2]
[(h6-C6Me6)Ru(DMPP)(2VP)Cl]PF6 [4+2]
[(h6-p-MeC6H4CHMe2)Ru(DMPP)(DPVP)Cl]PF6 [4+2]
[(h6-p-MeC6H4CHMe2)Ru(DMPP)(PVS)Cl]PF6 [4+2]
[(h6-p-MeC6H4CHMe2)Ru(DMPP)(PVSO)Cl]PF6 [4+2]
[(h6-p-MeC6H4CHMe2)Ru(DMPP)(MVK)Cl]PF6 [4+2]
[(h6-p-MeC6H4CHMe2)Ru(DMPP)(DMAA)Cl]PF6 [4+2]
[(h6-p-MeC6H4CHMe2)Ru(DMPP)(2VP)Cl]PF6 [4+2]
[(h6-C6H6)Ru(DMPP)(DPVP)Cl]PF6 [4+2]
[(h6-C6H6)Ru(DMPP)(PVS)Cl]PF6 [4+2]
[(h6-C6H6)Ru(DMPP)(2VP)Cl]PF6 [4+2]
[(h6-MeC6H5)Ru(DMPP)(DPVP)Cl]PF6 [4+2]
[(h6-MeC6H5)Ru(DMPP)(PVS)Cl]PF6 [4+2]
[(h6-MeC6H5)Ru(DMPP)(2VP)Cl]PF6 [4+2]
[(h6-C6Me6)Ru(DMPP)(ADPP)Cl]PF6 [4+2]
[(h6-p-MeC6H4CHMe2)Ru(DMPP)(ADPP)Cl]PF6 [4+2]
This work
This work
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(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
(19)
(20)
0.98 (163)
1.10 (216)
1.15 (166)
1.24 (112)
1.24 b
1.14 b
1.30 b
1.16 (191)
1.06 (123)
1.20 (147)
a In CH2Cl2 containing 0.1 M TBAP at 25°C, w=250 mV s−1. E values are vs. F+c /Fc. Cp=h5-C5H5.
b Epa only.
For the analogous reactions of the h5-Cp complexes
(reactions 1–3) the % DEs were much lower (15.4, 58.4,
and 0%, respectively) and in reactions 1 and 2 the
major diastereomer is A. From these results it appears
that diastereomer A should in general be the thermody-
namically favored diastereomer unless the steric interac-
tions between the h6-arene and the PPh2 group on the
2-position of the norbornene ring become quite large, in
which case diastereomer B will be favored. For the
products of the reactions involving PVSO (3a, 3b, and
9) and compounds 8a and 8b (L=PVS) diastereomer B
was the major diastereomer formed. For all other prod-
ucts diastereomer A was formed exclusively at the limit
of detection by 31P{1H}-NMR spectroscopy. Com-
pound 3a forms as the racemic diastereomers
(SLSSSRu–RLRSRRu), 3b as the racemic diastereomers
,
the RuꢁP1 distance (2.294 A), ave.) is slightly shorter
,
than the RuꢁP2 distance (2.327 A, ave.). Comparing the
RuꢁP1 distances in 1 with 19 and 7 with 20 we note that
upon chelate ring formation the RuꢁP1 bond distance
shortens slightly as expected. If these complexes were
ideally octahedral, the sum of the P1ꢁRuꢁP2, P1ꢁRuꢁCl,
and P2ꢁ RuꢁCl angles would be 270°. These angle sums
increase in the sequence: h6-C6Me6 (256.27°)Bh6-p-
MeC6H4CHMe2 (257.71°)Bh6-MeC6H5 (259.54°)$h6-
C6H6 (259.42°) in concert with the steric bulk of the
arene decreasing in the same order. Another measure of
the steric interaction between the arene and the sub-
stituents on the 7-phosphanorbornene ring is the dihe-
dral angle between the arene and P1P2Cl planes. These
dihedral angles decrease in the sequence: h6-C6Me6
(5.6°)\h6-p-MeC6H4CHMe2 (2.9°)\h6-C6H6 (0.5°)$
h6-MeC6H5 (0.2°). The percent diastereomeric excesses
(%DE=%major diastereomer−%minor diastereomer),
determined by 31P{1H}-NMR spectroscopy of the crude
products (Table 2) fall in the order: h6-C6H6 (\
(SLRSSRu–RLSSRRu), and
9 as the racemic dia-
stereomers (SLSSSRu–RLRSRRu).
4.2. Spectral characterization
99%)\h6-p-MeC6H4CHMe2
(87.8%)$h6-MeC6H5
(86%)\h6-C6Me6 (82%) suggesting that the% DE de-
We have previously noted [15] that when two
diastereomers of the DMPP/DPVP Diels–Alder cy-
creases roughly as the steric bulk of the arene increases.

198
K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
cloadducts are formed that diastereomer A may be
distinguished from diastereomer B by 31P{1H}-NMR
spectroscopy. In general the chemical shift difference of
the phosphorus resonances, Dl=lP7−lP2 is greater
for diastereomer A than for diastereomer B. As the
data in Table 2 show, except for 1a and 1b, where these
differences are essentially the same, this criterion still
holds. For all other complexes, when two diastereomers
were observed, the 31P{1H} chemical shift for
The spectra of the MVK adducts exhibit w(CO) near
1700 cm−1 as compared to that of the free ligand (1717
cm−1) supporting oxygen coordination as in the crystal
structures.
4.3. Redox properties of the complexes
The electron-donor abilities of coordinated ligands
and the complex geometry affect the redox properties
of ruthenium complexes. [17] The electrochemical be-
havior of the complexes prepared in this study was
investigated by cyclic voltammetry (Table 7). For all
complexes the Ru(II)–Ru(III) redox couple is a quasi-
reversible one-electron process or a process that ap-
proaches reversiblity. For 1, 2, 3, 5, 6, 7, 8, 9, 11, 12,
13, 18, 19, and 20, the follow-up chemical step is slow
and reversible voltammograms were observed. For the
other complexes, the follow-up chemical step is fast as
no cathodic wave could be seen on the return sweep,
even at high scan rates. The data in Table 7 are very
similar to those reported [13] for Ru(DMPP) (CO)Cl2
complexes of some of these ligands. The Ru(II)–
Ru(III) potentials ranged from 0.56 to 1.15 V for the
carbonyl complexes. The E1/2 values depend principally
upon the s-donor and/or p-acceptor abilities of the
ligands. Comparison of the E1/2 values of the h5-C5H5
and h6-arene complexes shows that oxidation of the
h5-C5H5 complexes occurs at lower potentials than for
analogous h6-arene complexes. Among the h6-arene
complexes the ease of oxidation generally decreases in
the sequence h6-C6Me6\h6-p-MeC6H4CHMe2\h6-
MeC6H5$h6-C6H6. Thus, the donor abilities of these
ligands toward Ru(II) decreases in the order h5-
C5H5\h6 - C6Me6\h6 - p - MeC6H4CHMe2\h6 - Me-
C6H5$h6-C6H6. The s-donor abilities of the 2-substi-
tuted-7- phosphanorbornenes are generally in the order
PꢀS\NꢀO as determined from the comparative
E1/2 values. Comparing the E1/2 values of 1 with 19 and
7 with 20 shows that chelate ring formation increases
the donor ability slightly.
diastereomer
A
occurs downfield of that for
diastereomer B.
1
The H and 13C chemical shifts of the 7-phosphanor-
bornene ring nuclei are also diagnostic of the nature of
the diastereomer formed. For convenience of discussion
these data are collected in Tables 5 and 6, respectively.
As can be seen in Fig. 3 protons 1, 3, 4, and 5 and all
the ring carbons are in considerably different environ-
ments for the two diastereomers. Considering com-
pounds 3a and 3b, which are diastereomers B and A,
respectively, we note that the chemical shifts of protons
1–5 for diastereomers A all occur downfield of the
corresponding resonances for diastereomer B. Compar-
ing the data for compounds 3 with 9 and 2, 8 and 14
with 17, and 4 with 10, and 5 with 11, and 6, 12, and 15
with 18 we note that the nature of the diastereomer has
a greater influence on these chemical shifts than does
either the nature of the arene or the 2-substituent. The
relative chemical shifts of protons 1 and 5 are particu-
larly diagnostic. Except for the four PVS adducts (2, 8,
14, and 17) the chemical shifts of proton-1 are
downfield of those of proton-5 for diastereomer B and
the converse is true for diastereomer A. Similar rela-
tionships are observed for the relative chemical shifts of
the methyl proton [CH3(5) and CH3(6)] resonances.
These chemical shift differences most likely arise be-
cause of the location of these nuclei in either the
shielding or deshielding regions of the magnetically
anisotropic arene rings. Similar arguments apply to the
relative 13C chemical shifts of the norbornene ring
carbons (C1 and C4, C5 and C6) and the two methyl
carbons (Table 6). The PVS adducts undergo epimeri-
zation at sulfur on the NMR time scale [1d], as evi-
denced by broad resonances for some of the phenyl
carbons in their 13C{1H}-NMR spectra. This dynamic
process has an effect on these relative chemical shifts.
With this body of data, X-ray crystallography and
multinuclear NMR spectroscopy, it is now possible to
identify the diastereomer by multinuclear NMR
spectroscopy.
4.4. Conclusions
The [(h6-arene)Ru(DMPP)Cl2] complexes undergo
intramolecular [4+2] Diels–Alder cycloaddition reac-
tions with a greater variety of dieneophiles than any
previously investigated complexes. In general, the
diastereoselectivities of these reactions are quite high. It
is lowest with the sulfur donors PVS and PVSO and
this may be related to the fact that sulfur also becomes
a stereocenter in the products derived from these two
dieneophiles. The diastereoselectivity of these Diels–
Alder cycloaddition reactions is under thermodynamic
control. The most favored diastereomer is formed such
as to minimize intramolecular steric interactions. These
new [(h6-arene)Ru(AB)Cl]PF6 complexes are currently
The infrared spectra of all these complexes exhibit
w(PF) vibrations at 838 and 557 cm−1 as expected for
−
PF6
salts. The spectra of the DMAA and PVSO
adducts exhibit w(CO) and w(SO) near 1590 and 1080
cm−1, respectively supporting sulfur and oxygen coor-
dination, respectively [16], for these potentially am-
bidentate ligands, as found in the crystal structures.

K.D. Redwine, J.H. Nelson / Journal of Organometallic Chemistry 613 (2000) 177–199
199
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being tested as catalysts for transfer hydrogenation of
ketones, alkenes and imines.
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5. Supplementary material
Tables of X-ray data in CIF format for compounds
1, 2, 3a, 3b, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18,
19 and 20 have been deposited with the Cambridge
Crystallographic Data Centre, CCDC nos. 144240–
144259. Copies of this information may be obtained
free of charge from The Director, CCDC, 12 Union
Road, Cambridge, CB2 1EZ, UK (Fax: +44-1223-
336033; e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
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Acknowledgements
This research was supported by an award from the
Research Corporation for which we are grateful. We
are also grateful to the National Science Foundation
(Grant no. CHE-9214294) for funds to purchase the
500 MHz NMR spectrometer.
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