Synthesis of metallocenes of zirconium, hafnium, manganese, iron, tin, lead and half-sandwich complexes of rhodium and iridium containing the ligands (η-C5R4CR′2PMe2), where R and R′ may be H or Me

Article abstract of DOI:10.1016/S0022-328X(01)01175-5

The dimethylphosphino substituted cyclopentadienyl precursor compounds [M(C₅Me₄CH₂PMe₂)], where M=Li⁺ (1), Na⁺ (2), or K⁺ (3), and [Li(C₅H₄CR′₂PM

Full text of DOI:10.1016/S0022-328X(01)01175-5

Journal of Organometallic Chemistry 640 (2001) 93–112
www.elsevier.com/locate/jorganchem
Synthesis of metallocenes of zirconium, hafnium, manganese, iron,
tin, lead and half-sandwich complexes of rhodium and iridium
containing the ligands (h-C5R4CR%PMe2), where R and R%
2
may be H or Me
Ronan M. Bellabarba a, Gerald P. Clancy a, Pedro T. Gomes b, Ana M. Martins b,
Leigh H. Rees a, Malcolm L.H. Green a,*
a Wolfson Catalysis Centre, Inorganic Chemistry Laboratory, South Parks Road, Oxford OX1 3QR, UK
b Centro de Qu´ımica Estrutural, Complexo I, Instituto Superior Te´cnico, A6. Ro6isco Pais, 1049-001 Lisbon, Portugal
Received 31 May 2001
This paper is dedicated to Professor Alberto Dias on the occasion of his 60th birthday
Abstract
The dimethylphosphino substituted cyclopentadienyl precursor compounds [M(C5Me4CH2PMe2)], where M=Li+ (1), Na+ (2),
or K+ (3), and [Li(C5H4CR%2PMe2)], where R%2=Me2 (4), or (CH2)5 (5), [HC5Me4CH2PMe2H]X, where X−=Cl− (6) or PF6− (7)
and [HC5Me4CH2PMe2] (8), are described. They have been used to prepare new metallocene compounds, of which representative
examples are [Fe(h-C5R4CR2%PMe2)2], where R=Me, R%=H (9); R=H and R2% =Me2 (10), or (CH2)5 (11), [Fe(h-
C5H4CMe2PMe3)2]I2 (12), [Fe{h-C5Me4CH2P(O)Me2}2] (13), [Zr(h-C5R4CR2%PMe2)2Cl2], where R=H, R%=Me (14), or R=Me,
R%=H (15), [Hf(h-C5H4CMe2PMe2)2]Cl2] (16), [Zr(h-C5H4CMe2PMe2)2Me2] (17), {[Zr(h-C5Me4CH2PMe2)2]Cl}{(C6F5)3-
BClB(C6F5)3} (18), [Zr{(h-C5Me4CH2PMe2)2Cl2}PtI2] (19), [Mn(h-C5Me4CH2PMe2)2] (20), [Mn{(h-C5Me4CH2PMe2B(C6F5)3}2]
(21), [Pb(h-C5H4CMe2PMe2)2] (23), [Sn(h-C5H4CMe2PMe2)2] (24), [Pb{h-C5H4CMe2PMe2B(C6F5)3}2] (25), [Pb(h-
C5H4CMe2PMe2)2PtI2] (26), [Rh(h-C5Me4CH2PMe2)(C2H4)] 29, [M(h,kP-C5Me4CH2PMe2)I2], where M=Rh (30), or Ir, (31).
© 2001 Elsevier Science B.V. All rights reserved.
Keywords: Functionalised metallocene compounds; Chelating cyclopentadienyl-phosphine ligands; Chelating cyclopentadienyl-phosphine com-
plexes; Bimetallic complexes; Derivatised ferrocenes; Derivatised manganocenes
compound could act as a chelating diphosphine ligand
to a Mo(CO)4 moiety to form the heterobimetallic
system {[Ti{h-C5H4(CH2)2PPh2}2Cl2]Mo(CO)4}.
1. Introduction
Metallocenes containing tertiary phosphine ligands
attached to the cyclopentadienyl rings, in the general
class [h-C5R4(CR%) PR¦], where n=0, 1, 2 or 3, R=H
or alkyl, R%=H, alkyl or aryl, R¦=alkyl or aryl, have
been long known. There are various methods for the
synthesis of the tertiary phosphine substituted cy-
clopentadienyl ligand precursors [1–5].
Since then many mono- and bis-h-cyclopentadienyl-
tertiary phosphine compounds have been prepared [7–
12,18b]. Representative examples are: the ruthenium
complexes [Ru(h,kP-C5H4CH2CH2PPh2)(L)Cl], where
L=PPh3 and P(OMe)3], and [Ru(h,kP-C5H4CH2CH2-
PPh2)(PPh3)[(+)-NH2C(Me)Ph]}BF4 [13], the cobalt
compounds [Co(h,kP-C5H4CH2CH2PPh2)L], where
L=CO, C2H4 [14–17], the rhodium and iridium com-
pounds [M(h,kP-C5H4CH2CH2PPh2)I2], where M=Rh
and Ir [18] and the zirconocene compounds
[Zr(h-C5H4CMe2PPh2)2X2] [19], where X=Cl or Me.
The compound [Zr(h-C5H4CMe2PPh2)2Me2] undergoes
2 n
2
The first metallocene to contain such a ligand was
[Ti{h-C5H4(CH2)2PPh2}2Cl2] [6]. It was shown that this
* Corresponding author. Tel.: +44-1865-272649; fax: +44-1865-
272690.
E-mail address: malcolm.green@chem.ox.ac.uk (M.L.H. Green).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01175-5

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R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
abstraction of one methide (CH−3 ) group on treatment
with [B(C6F5)3] to form the cationic species [Zr(h-
C5H4CMe2PPh2)2Me][BMe(C6F5)3] which is stabilised
by intramolecular bonding of both the PPh2 groups to
the zirconium centre [19a].
2. Results and discussion
New metallocenes containing the dimethylphosphi-
noalkyl-h-cyclopentadienyl ligands in the general class
(h-C5R4CR%PMe2), where R, R% may be H or Me, have
2
been prepared. The ligand precursors which have been
synthesised may be organised into anionic, cationic and
neutral compounds. The anionic salts are M[C5Me4-
CH2PMe2], where M=Li+ (1), Na+ (2), or K+ (3);
and [Li(C5H4CR%PMe2)], where R% =Me2 (4), or
(CH2)5 (5). The cationic salts are [HC5Me4CH2-
PMe2H]X, where X−=Cl− (6) or PF−6 (7). The neutral
compound [HC5Me4CH2PMe2] (8), prepared by treat-
ment of compound 7 with a methanol solution of
potassium hydroxide, is a water-stable, air-sensitive,
pale-yellow oil soluble in pentane, toluene, benzene,
THF and diethyl ether.
The ligand syntheses are exemplified in Scheme 1 and
in Section 3. The analytical and spectroscopic data
which characterise the ligand precursor compounds 1–
8, and all the other new compounds described in this
work, are given in Table 1. Compounds 1–5 and 8 were
handled under an atmosphere of dry dinitrogen,
whereas 6 and 7 are air-stable; the anionic systems are
especially sensitive to oxygen and water.
Studies by Butenschon et al. have demonstrated the
capability of the phosphine group on these bifunctional
ligands to selectively bind to the metal centre [Zr(h-
C5H4CR2PAr2)2R%], R%=Cl or Me [12,14–17]. When
2
2
2
R%=Me, treatment with [B(C6F5)3] gives mononuclear
dications with intramolecular bonding of the
PAr2 group to the metal centre, as in [Zr(hkP-
C5H4CR2PAr2)2][MeB(C6F5)3]2 [19].
Many heterobimetallic compounds combining bis-h-
cyclopentadienyl derivatives of Group 4 metals contain-
ing alkyl- or aryl-phosphino substituents react as
diphosphine ligands with later transition metals [1,20–
22,54a]. For example, treatment of [Mo(nbd)(CO)4]
with the bidentate ligand [Zr(h-C5H4PPh2)2Cl2] results
in the isolation of the heterobimetallic complex [{Zr(h-
C5H4PPh2)2Cl2}Mo(CO)4] [1,3].
Similar heterobimetallic compounds are formed by
the compounds [Ti(h-C5H4CH2CH2PPh2)2Cl2] and
[Zr(h-C5H4CH2CH2PPh2)2Cl2]. The compound [Zr(h-
C5H4CMe2PAr2)2Cl2] reacts with [MCl2(NCPh)2],
where M=Pd and Pt, to give the bimetallic complexes
[{Zr(h-C5H4CMe2PAr2)2Cl2}MCl2] (M=Pd, Pt; Ar=
Ph, p-tolyl) [3]. The NMR data indicated a trans-struc-
ture [4,23–26].
The zirconocene [Zr(h-C5Me4PMe2)2Cl2] reacts with
[Ru(H2)H2(PPh3)3] to give the compounds [ZrCl(h-
C5Me4PMe2)2(m-H)(m-Cl)RuH(PPh3)] and [ZrCl(h-
C5Me4PMe2)2(m-H)2RuCl(PPh3)] [27]. Related bimetal-
lic compounds of Pd, Pt, Rh and Ir have been described
[21,28,29].
A selection of the salts containing the dimethylphos-
phinoalkylcyclopentadienide anions were reacted with
ferrous chloride to give functionalised ferrocenes in the
class bis(dimethylphosphinoalkyl-h-cyclopentadienyl)-
iron namely, [Fe(h-C5R4CR%PMe2)2], where R=Me,
2
R%=H (9); R=H and R% =Me2 (10) or (CH2)5 (11).
2
These new ferrocenes are shown in Scheme 2. Treat-
ment of compound 10 with methyliodide gave the air-
stable trimethylphosphonium derivative [Fe(h-C5H4-
CMe2PMe3)2]I2 (12).
Addition of ferrous chloride to a THF solution of 1
at −78 °C gave orange lozenges of [Fe(h-C5Me4CH2-
Scheme 1. (i) [Li(CH2PMe2)] in THF at −78 °C; then, HCl in Et2O, for X=Cl 6 90%; for X=PF6 7, add NH4PF6 to 6 in H2O, 85%. (ii)
X=PF6: add KOH in methanol, 45%. (iii) M[N(SiMe3)2] in THF at −78 °C, for 12 h. M=Li 1, 76%; M=Na 2, 57%; M=K 3, 79%.

R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
Table 1 (Continued)
95
Table 1
Analytical and spectroscopic data
Compound and analysis a
NMR data b
Compound and analysis a
NMR data b
[Li{C5H4C(CH2)5PMe2}] (5)
White powder
1H pyridine-d5
6.3 [s, 2H, CringH]
6.03 [s, 2H, CringH]
2.2-2.3 [m, 2H, ring CH2]
1.2-2.0 [m, 8H, ring CH2]
[Li(C5Me4CH2PMe2)] (1)
White
Very air sensitive
1H pyridine-d5
2.93 [s, 2H, CH2]
2.25 [s, 6H, CringCH3]
2.23 [s, 6H, CringCH3]
1.03 [s, 6H, P(CH3)2]
13C{1H} pyridine-d5
105.15 [s, CringCH3]
104.91 [s, CringCH3]
0.85 [d, 6H, P(CH3)2] 2JPH=3.5
13C{1H} pyridine-d5
103.0 [s, CringC] (2 quaternary
signals not detected)
102.4 [s, CringC]
33.5 [s, CH2]
28.5 [s, CH2]
22.8 [d, CH2] JPC=8.6
9.8 [d, P(CH3)2] 1JPC=20.2
31P {1H} pyridine-d5
−26.6 [s, P(CH3)2]
104.80 [s, Cipso
]
29.20 [d, CH2] JCP=7.76
13.37 [d, P(CH3)2] JCP=17.2
10.87 [s, CringCH3]
10.37 [s, CringCH3]
31P{1H} pyridine-d5
−52 [s, P(CH3)2]
[Na(C5Me4CH2PMe2)] (2)
White
C, 63.1 (66.0)
H, 9.2 (9.2)
1H pyridine-d5
[HC5Me4CH2PMe2H][Cl] (6)
White solid
1H acetone-d6
2.71 [d, 2H, CH2] 2JHP=1.5
2.22 [s, 6H, CringCH3]
2.17 [s, 6H, CringCH3]
0.86 [d, 6H, P(CH3)2]
2JHP=2.5
3.90 [t, 1H, CHb] 2JHbP=14.0,
2JHbHa=15.0
3.51 [t, 1H, CHa] 2JHaP=14.0,
P, 14.3 (14.2)
2JhaHb=15.0
13C{1H}- and 1H-NMR spectra
2.85 [m, 1H, HCringCH3]
Very air sensitive
13C{1H} pyridine-d5
105.58 [s, Cipso
105.59 [s, CringCH3]
105.34 [s, CringCH3] JCP=7.5
131.10 [d, CH2]
14.40 [d, P(CH3)2] JCP=16
12.40 [s, CringCH3]
were assigned using a 1H–13
C
]
correlation HMQC experiment
2.10 [d, 3H, P(CH3)2]
2JHP=14.5
2.06 [d, 3H, P(CH3)2]
2JHP=14.5
1.93 [s, 3H, CringCH3]
1.83 [s, 3H, CringCH3]
1.77 [s, 3H, CringCH3]
1.08 [d, 3H, HCringCH3]
3JHH=8.0
11.96 [s, CringCH3]
31P{1H} pyridine-d5
−46.0 [s, P(CH3)2]
[K(C5Me4CH2PMe2)] (3)
White
C, 57.9 (61.5)
H, 8.8 (8.6)
1H THF-d8
2.44 [d, 2H, CH2] 2JHP=1.5
1.85 [s, 6H, CringCH3]
1.84 [s, 6H, CringCH3]
0.92 [d, 6H, P(CH3)2]
2JHP=2.5
13C{1H} D2O
143.3 [s, Cring
134.3 [s, Cring
127.2 [s, Cring
127.1 [s, Cring
]
]
]
]
Very air sensitive
13C{1H} THF-d8
49.93 [s, HCringCH3]
17.96 [d, CH2] JPC=51.6
13.10 [s, HCringCH3]
107.93 [s, Cipso
]
107.13 [s, CringCH3]
106.44 [s, CringCH3] JCP=8.0
31.64 [d, CH2]
15.73 [d, P(CH3)2] JCP=17.0
12.06 [s, Cring CH3]
11.63 [s, Cring CH3]
31P{1H} THF-d8
11.14 [s, CH3Cring
10.83 [s, CH3Cring
]
]
9.97 [s, CH3Cring
]
2.93 [d, P(CH3)2] JPC=28.9
2.51 [d, P(CH3)2] JPC=28.9
31P{1H} acetone-d6
−45.4 [s, P(CH3)2]
40.38 [s, P(CH3)2H]
[Li(C5H4CMe2PMe2)] (4)
White
1H pyridine-d5
[HC5Me4CH2PMe2H][PF6] (7)
White solid
C, 42.2 (42.1)
1H acetone-d6
6.29 [s, 2H, CringH]
6.17 [s, 2H, CringH]
1.57 [d, 6H, P(CH3)2]
2JPH=15
5.80 [d,1H, HP(CH3)2]
3.69 [t, 1H, CHb] 2JHaP=14.0,
2JHaHb=15.0
H, 6.3 (6.5)
3.35 [t, 1H, CHa] 2JHaP=14.0
2JHaHb=15.0
0.97 [s, 6H, C(CH3)2]
13C{1H} pyridine-d5
123.74 [d, Cipso]
2JPC=5.5
P, 18.8 (18.1)
2.86 [q, 1H, HCringCH3]
3JHH=7.5
101.62 [s, Cring
101.54 [s, Cring
]
]
2.00 [d, 3H, P(CH3)2]
2JHP=13.5
1.92 [s, 3H, CringCH3]
31.49 [d, C(CH3)2] 2JPC=9
25.42 [d, C(CH3)2] 1JPC=19
9.53 [d, P(CH3)2] 1JPC=22.5
31P{1H} pyridine-d5
13C{1H}- and 1H-NMR spectra
were assigned using a 1H–13
C
correlation HMQC experiment
−28 [s, P(CH3)2]

96
R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
Table 1 (Continued)
Table 1 (Continued)
Compound and analysis a
NMR data b
Compound and analysis a
NMR data b
9.6 [s, CringCH3]
31P{1H} C6D6
1.88 [d, 3H, P(CH3)2]
2JHP=13.5
−50.0 [s, P(CH3)2]
1.86 [s, 3H, CringCH3]
1.80 [s, 3H, CringCH3]
1.07 [d, 3H, HCringCH3]
3JHH=15.0
[Fe(h-C5H4CMe2PMe2)2] (10)
Orange crystals
C, 60.80 (61.55)
1H C6D6
3.97 [m, 4H, CringH]
3.79 [m, 4H, CringH]
1.29 [d, 12H, P(CH3)2]
2JPH=14.0
13C{1H} acetone-d6
H, 8.15 (8.26)
143.2 [s, Cring
142.5 [s, Cring
134.3 [s, Cring
127.3 [s, Cring
]
]
]
]
0.60 [d, 12H, C(CH3)2]
3JPH=3.6
13C{1H} C6D6
50.7 [s, HCring ꢀCH3]
17.8 [d, CH2] JCP=46.5
13.8 [s, HCringCH3]
12.4 [s, CringCH3]
11.8 [s, CringCH3]
96.3 [s, Cring
67.4 [s, Cring
]
]
]
66.4 [d, Cipso
3JPC=1.7
31.3 [d, C(CH3)2] 1JPC=15.0
2
25.7 [d, C(CH3)2] JPC=20.0
11.3 [s, CringCH3]
1
10.2 [d, P(CH3)2] JPC=20.0
31P{1H} C6D6
3.32 [d, P(CH3)2] JCP=47.8
2.50 [d, P(CH3)2] JCP=47.8
19F acetone-d6
−18.5 [s, P(CH3)2]
[Fe{h-C5H4C(CH2)5PMe2}2] (11) 1H C6D6
−195.51 [d, PF6] JFP=710
Orange crystals
C, 65.9 (66.4)
H, 8.4 (8.6)
Fe, 11.7 (11.9)
P, 12.7 (13.2)
4.06 [s, 4H, CringH]
[HC5Me4CH2PMe2] (8)
Pale yellow oil
C, 76.3 (73.4)
1H C6D6
3.77 [s, 4H, CringH]
2.15–2.25 [m, 4H, ring CH2]
1.75–2.0 [m, 10H, ring CH2]
1.5–1.6 [m, 4H, ring CH2]
1.2–1.35 [m, 2H, ring CH2]
0.49 [d, 12H, P(CH3)2]
2JPH=4.0
2.85 [m, 1H, HCringCH3]
2.42 [dd, 1H, bridge CH]
2JPH=10, 4JH–H=3
2.31 [d, 1H, bridge CH]
2JPH=10
H, 8.3 (10.8)
1.79 [s, 3H. CringCH3]
1.77 [s, 3H, CringCH3]
1.75 [s, 3H, CringCH3]
1.07 [d, 3H, HCringCH3]
3JHH=7.5
13C{1H} C6D6
97.5 [s, CringH]
67.1 [s, CringH]
65.5 [s, CringH]
0.89 [d, 3H, PCH3] 2JPH=3
0.83 [d, 3H,, PCH3] 2JPH=2.5
13C{1H} C6D6
36.4 [d, Cring(CH2)5] JPC=21
34.3 [d, ring CH2] JPC=15
27.7 [s, ring CH2]
22.7 [d, ring CH2] 1JPC=12
9.1 [d, P(CH3)2] 1JPC=20
31P{1H} C6D6
138.6 [s, Cring
138.2 [s, Cring
135.8 [s, Cring
134.0 [s, Cring
]
]
]
]
−39.3 [s, PMe2]
50.42 [s, HCringCH3]
31.10 [d, CH2] JCP=10.0
14.57 [d, P(CH3)2] JCP=11.0
14.50 [s, HCringCH3]
14.46 [d, P(CH3)2] JCP=11.0
12.40 [s, CringCH3]
[Fe(h-C5H4CMe2PMe3)2I2] (12)
Yellow–orange microcrystals
C, 38.5 (39.2)
1H D2O
4.42 [s, 4H, CringH]
4.34 [s, 4H, CringH]
1.54 [d, 12H, C(CH3)2]
2JPH=17.1
H, 5.3 (5.7)
MS (electrospray) m/z 547.2
[M+H−I]+
1.50 [d, 18H, P(CH3)2]
11.79 [s, CringCH3]
2JPH=13.2
11.22 [s, CringCH3]
m/z 421.3 [M+H−2I]+
31P{1H} D2O
31P{1H} C6D6
39.2 [s, PMe2]
−45.9 [s, P(CH3)2]
[Zr(h-C5H4CMe2PMe2)2Cl2] (14) 1H CD2Cl2
White crystalline
C, 42.5 (43.4)
H, 6.2 (5.9)
[Fe(h-C5Me4CH2PMe2)2] (9)
Orange crystals
C, 64.9 (64.6)
H, 9.5 (9.0)
P, 13.9 (13.9)
1H C6D6
2.27 [br s, 4H, CH2]
6.40 [s, 2H, CringH]
6.35 [s, 2H, CringH]
1.54 [d, 6H, P(CH3)2]
2JPH=13.5
1.74 [s, 12H, CringCH3]
1.63 [s, 12H, CringCH3]
0.83 [d, 12H, P(CH3)2] 2JPH=3
13C{1H} C6D6
80.0 [d, CringC] JPC=10.7
79.2 [s, CringC]
78.1 [d, CringC] JPC=1.5
28.9 [d, PCH2] 1JPC=13.5
14.5 [d, P(CH3)2] 1JPC=16
10.6 [d, CringCH3] JPC=2.5
P, 10.6 (10.6)
0.73 [d, 6H, C(CH3)2]
Fe, 12.0 (12.0)
3JPH=3.5
Zr, 15.5 (15.7)
Cl, 23.6 (24.4)
MS (EI) m/z 494/496/498
13C{1H} CD2Cl2
138.5 [Cring]
113.9 [d, Cring
]
]
3JPC=22
3JPC=18
111.6 [d, Cring
33.4 [d, C(CH3)2] 1JPC=16
21.9 [C(CH3)2]

R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
Table 1 (Continued)
97
Table 1 (Continued)
Compound and analysis a
NMR data b
Compound and analysis a
NMR data b
8.60 [d, P(CH3)2,] 1JPC=21
31P{1H} CD2Cl2
−10.8 [s, P(CH3)2]
{[Zr(h-C5Me4CH2PMe2)2]Cl}-
{(C6F5)3BClB(C6F5)3} (18)
Pale yellow
1H toluene-d8
2.52 [d, 2H, CH2] 2JHP=7.0
1.66 [s, 6H, CringCH3]
1.65 [s, 6H, CringCH3]
0.62 [d, 6H, P(CH3)2]
2JHP=10.6
[Zr(h-C5Me4CH2PMe2)2Cl2] (15) 1H pyridine-d5
Pale yellow
C, 49 8 (52.1)
H, 7.30 (7.29)
P, 11.1 (11.2)
2.52 [s, 2H, CH2]
1.81 [s, 6H, CringCH3]
1.65 [s, 6H, CringCH3]
0.62 [s, 6H, P(CH3)2]
19F toluene-d8
−163.0 [m, 1F, p-C6F5]
−158.0 [m, 2F, m-C6F5]
−133.0 [m, 2F, o-C6F5]
13C{1H} toluene-d8
149.2 [d, o-C6F5] JCF=247
140.7 [d, p-C6F5] JCF=252 1
37.8 [d, m-C6F5] JCF=257
124.4 [s, CringCH3]
123.4 [s, CringCH3]
118.0 [d, Cipso
115.4 [s, Cipso
22.4 [d, CH2] JCP=31.4
13.9 [s, CringCH3]
11.6 [s, CringCH3]
Zr, 17.4 (16.5)
MS (FAB) m/z 547 [M−Cl+2O]
50%
The analysis suggests the
compound has been oxidised
during storage. This explains the
MS. Theoretical values for
[Zr(h-C5Me4CH2P(O)Me2)2Cl2]
are: C, 49.31; H, 5.47; P, 10.60;
Zr, 15.60
13C{1H} pyridine-d5
]
2JCP=7.25
]
125.3 [d, Cipso]
2JCP=12.9
111.7 [s, CringCH3]
121.6 [s, CringCH3]
7.89 [d, P(CH3)2] JCP=36.7
11B{1H} toluene-d8
−13.0 [s, B(C6F5)3]
31P{1H} toluene-d8
8.26 [s, P(CH3)2]
30.1 [d,CH2] JCP=14.0
13.25 [d, P(CH3)2] JCP=15.0
11.6 [d, CringCH3] 4JCP=4.2
10.5 [s, CringCH3]
31P{1H} pyridine-d5
−44.5 [s, P(CH3)2]
[Zr(h-C5Me4CH2PMe2)2Cl2PtI2]
31P{1H} THF-d8
(19)
[Hf(h-C5H4CMe2PMe2)2Cl2] (16) 1H C6D6
Yellow–orange
−12.0 [s, P(CH3)2] Pt satellites
PPt=2304
Cream solid
C 41.7 (41.2)
H 5.6 (5.5)
6.26 [m, 4H, CringH]
6.25 [m, 4H, CringH]
J
C, 28.5 (28.8)
H, 4.1 (4.5)
MS (FAB) m/z 747 [M−2I] 50%
1.50 [d, 6H, P(CH3)2] 2JPH=14
0.65 [d, 12H, C(CH3)2] 3JPH=4
13C{1H} C6D6
P 10.6 (10.6)
2JPC=5
3JPC=4
[Mn(h-C5Me4CH2PMe2)2] (20)
Orange crystals
C, 62.8 (64.7)
1H C6D6
138.7 [d, Cring
114.2 [d, Cring
]
]
4.96 [s, 6H, P(CH3)2]
−2.51 [br s, 6H, CringCH3]
−4.21 [br s, 6H, CringCH3]
−11.29 [br s, 2H, CH2]
31P{1H} toluene-d8
112.1 [s, Cring
]
35.1 [d, C(CH3)2] 2JPC=16
23.6 [d, C(CH3] 1JPC=17
10.7 [d, P(CH3)2] 1JPC=21
31P{1H} C6D6
H, 10.4 (9.1)
P, 13.6 (13.9)
MS (FAB) m/z 445 [M+] 50%
210.0 [s, P(CH3)2]
−8.0 [s, P(CH3)2]
[Mn{(h-C5Me4CH2PMe2B-
(C6F5)3}2] (21)
Yellow–orange
[Zr(h-C5H4CMe2PMe2)2Me2] (17) 1H CD2Cl2
White microcrystals
C, 55.5 (57.9)
H, 8.4 (8.4)
6.06 [m, 4H, CringH]
C, 42.5 (42.8)
H, 6.36 (6.36)
6.02 [m, 4H, CringH]
1.29 [d, 12H, P(CH3)2]
2JPH=13.5
0.76 [d, 12H, C(CH3)2]
3JPH=4.0
MS (FAB) m/z 1469 [M+] 5%
m/z 957 [M−B(C6F5)3] 10%
m/z 445 [M-2 B(C6F5)3] 100%
Zr, 20.0 (20.0)
[Pb(h-C5H4CMe2PMe2)2] (23)
Orange crystals
C, 43.2 (44.4)
1H toluene-d8
−0.26 [s, 6H, Zr(CH3)2]
13C{1H} C6D6
134.0 [d, Cring] JPC=5.5
5.73 [m, 2H, CringH]
5.68 [m, 2H, CringH]
1.22 [d, 6H, P(CH3)2]
2JHP=12.0
H, 6.0 (6.0)
110.0, [s, Cring
]
108.8 [d, Cring] JPC=4.0
33.8 [d, C(CH3)2] 2JPC=14.5
31.4 [s, Zr(CH3)2]
24.0 [d, C(CH3)2] 1JPC=18.5
10.4 [d, P(CH3)2] 1JPC=20.0
31P{1H} CD2Cl2
0.77 [d, 6H, C(CH3)2]
3JHP=3.5
13C{1H}- and 1H-NMR spectra
31P{1H} toluene-d8
were assigned using a 1H–13
C
correlation HMQC experiment
−15.6 [s, P(CH3)2] 3JPPb=276
207Pb{1H} toluene-d8
−12.0 [s, P(CH3)2]

98
R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
Table 1 (Continued)
Table 1 (Continued)
Compound and analysis a
NMR data b
Compound and analysis a
NMR data b
−4925.2 [t, Pb] 3JPbP=270
13C{1H} toluene-d8
Pb, 19.8 (20.9)
MS (FAB) m/z 863 [M−I] 40%,
m/z 736 [M−2I] 25%
139.5 [s, Cipso
]
109.4 [d, CringH] JCPb=106
108.8 [d, CringH] JCPb=82
31.7 [d, C(CH3)2] JCP=16
26.8 [d, P(CH3)2] JCP=13
11.8 [d, C(CH3)2] 2JCP=21
[Rh(h,kP-C5Me4CH2PMe2)-
(C2H4)] (29)
Yellow–brown
C, 51.47 (51.55)
H, 7.28 (7.42)
1H C6D6
3.36 [d, 2H, CH2] 2JPH=8.6
2.17 [s, 6H, CringCH3]
2.01 [d, 6H, CringCH3]
4JPH=3.2
1.86 [d, 6H, P(CH3)2] 2JPH=13
31P{1H} C6D6
[Sn(h-C5H4CMe2PMe2)2] (24)
Yellow
C, 51.6 (53.0)
1H toluene-d8
P, 9.16 (9.49)
Rh, 30.19 (31.54)
5.67 [m, 2H, CringH]
5.62 [m, 2H, CringH]
1.26 [d, 3H, P(CH3)2]
2JHP=11.5
−29.6.[d, P(CH3)2]
H, 7.3 (7.1)
JRhP=198.4
0.74 [d, 6H, C(CH3)2]
3JHP=3.5
[Rh(h,kP-C5Me4CH2PMe2)I2] (30) 1H toluene-d8
Brown
3.91 [d, 2H, CH2] 2JPH=8.7
13C{1H}- and 1H-NMR spectra
119Sn{1H} toluene-d8
C, 25.98 (26.11)
H, 3.60 (3.65)
2.19 [s, 6H, CringCH3]
2.01 [d, 6H, CringCH3]
4JPH=2.8
were assigned using a 1H–13
C
correlation HMQC experiment
−2162.8 [t, Sn] 3JSn–P=110
13C{1H} toluene-d8
P, 5.02 (5.61)
1.88 [d, 6H, P(CH3)2]
2JPH=11.6
31P{1H} C6D6
140.0 [s, Cipso
]
I, 42.14 (46.12)
109.9 [s, CringH]
107.9 [s, CringH]
Rh, 17.21 (18.64)
−22.2.[d, P(CH3)2]
JRhP=136.8
31.8 [d, C(CH3)2] JCP=16
26.6 [d, P(CH3)2] 4JCSn117=360
4JCSn119=180; JCP=13
10.0 [d, C(CH3)2] 3JCSn117=471
3JCSn119=230; 2JCP=21
31P{1H} toluene-d8
[Ir(h,kP-C5Me4CH2PMe2)I2] (31) 1H CD2Cl2
Brown
3.89 [d, 2H, CH2] 2JPH=8.6
C, 22.06 (22.48)
H, 3.11 (3.14)
2.15 [s, 6H, CringCH3]
2.08 [d, 6H, CringCH3]
4JPH=3.3
−21.4 [s, P(CH3)2] 3JPSn=111
P, 4.39 (4.83)
1.81 [d, 6H, P(CH3)2]
2JPH=12.9
31P{1H} CD2Cl2
−27.5.[s, P(CH3)2]
[Pb{h-C5H4CMe2PMe2B-
(C6F5)3}2] (25)
Yellow
C, 42.5 (42.7)
H, 2.6 (2.1)
1H pyridine-d5
I, 35.76 (39.58)
Ir, 28.22 (29.97)
5.84 [m, 2H, CringH]
5.82 [m, 2H, CringH]
1.13 [d, 6H, P(CH3)2]
2JHP=12.0
0.65 [d, 6H, C(CH3)2]
3JHP=3.0
11B{1H} pyridine-d5
0.61 [d, (C6F5)3BPMe2]
a Analytical data given as: found (calculated)%.
b Room temperature. Data given as: chemical shift (l),
[multiplicity (s=singlet, d=doublet, t=triplet, m=multiplet,
br=broad), relative intensity, assignment], and coupling constant
(in Hz).
P, 3.43 (3.96)
PMe2)2] (9) in 45–49% yield. Crystals of 9 suitable for
X-ray diffraction were grown by evaporation of a ben-
zene-d6 solution. The crystal structure of 9 has been
determined and the molecular structure is shown in Fig.
1. Selected interatomic distances and bond angles are
shown in Table 2. A solution of 9 in perdeuterobenzene
was exposed to air for 72 h to give crystals of [Fe{h-
C5Me4CH2P(O)Me2}2] 13. The crystal structure of 13
has been determined and the molecular structure is
shown in Fig. 2. Selected distances and angles are given
in Table 3.
J
BP=70.5
13C{1H} pyridine-d5
149.5 [br, C6F5]
147.5 [br, C6F5]
139.4 [br, C6F5]
116.3 [s, Cipso
109.5 [s, CringH]
108.4 [s, CringH]
32.12 [d, C(CH3)2] JCP=11.8
26.82 [d, P(CH3)2] JCP=15.9
10.94 [d, C(CH3)2] 2JCP=19.6
3P{1H} pyridine-d5
]
−11.6 [s, P(CH3)2]
Comparison of the structures of 9 and 13, shows that
the bond lengths and angles of the ferrocene skeletons
seem to be relatively unaffected by the oxidation of the
tertiary phosphine. The FeꢀCCp distance in 9 is 2.0517
[Pb(h-C5H4CMe2PMe2)2PtI2] (26) 31P{1H} THF-d8
Yellow–orange
−4.67 [s, P(CH3)2] Pt satellites
JPPt=2320
C, 25.1 (24.3)
H, 3.6 (3.3)
P, 6.4 (6.3)
,
,
A, whilst in 13 it is 2.042 A. The two rings are slightly
eclipsed, as shown by the angles between opposite
carbon atoms through the metal centre (177.71 and

R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
99
Scheme 2. (i) For R=H, R%2=(CH2)5: anhydrous FeCl2 in THF at room temperature, ca. 15%. (ii) For R=H, R%=Me: anhydrous FeCl2 in
THF at −78 °C; warm to room temperature, 21%. (iii) MeI in pentane for 5 h, \90%. (iv) For R=Me, R%=H: anhydrous FeCl2 at −78 °C,
46–49%. (v) Expose to air for 2 days.
174.8°, respectively, for 9 and 13). The tertiary phos-
phine fragments of the two complexes are more affected
by the oxidation. The length of the PꢀMe bond, for
Addition of half an equivalent of anhydrous ferrous
chloride to mixture formed from 6,6-(pen-
a
tamethylene)fulvene and LiPMe2, followed by stirring
overnight, yields an orange solution. Orange crystals of
[Fe{h-C5Me4C(CH2)5PMe2}2] (11) suitable for X-ray
diffraction were obtained and the molecular structure
and selected data are given in Fig. 3 and Table 4,
respectively.
,
,
instance, decreases from 1.829 A in 9 to 1.760 A in 13.
Similarly, the PꢀCH2 bond length decreases from 1.856
,
to 1.792 A.
The cyclohexyl ring of 11 appears to modify the
angle between the Cp ring and the phosphorus atom:
compared to 9 and 13, where the effect of the sub-
stituents on the bridge can be assumed to be minimal,
the CpꢀCꢀPMe2 angle is 112.05(13) and 113.3(4)°, re-
Table 2
,
Selected bond lengths (A) and bond angles (°) for 9
Bond lengths
Fe(1)ꢀC(1)
C(1)ꢀC(2)
C(9)ꢀC(10)
P(1)ꢀC(10)
P(1)ꢀC(11)
2.0517(16)
1.434(2)
1.502(2)
1.8562(18)
1.829(2)
Bond angles
C(1)ꢀFe(1)ꢀC(24)
P(1)ꢀC(10)ꢀC(1)
C(10)ꢀP(1)ꢀC(11)
Fe(1)ꢀC(1)ꢀC(2)
177.71(7)
112.05(13)
99.40(9)
69.59(9)
Fig. 1. Molecular structure of 9.

100
R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
Treatment of zirconium tetrachloride with a selection
of the salts of dimethylphosphinoalkylcyclopentadi-
enide anions gave the corresponding dimethylphosphi-
noalkylcyclopentadienylzirconocene derivatives {[Zr(h-
C5R4CR%PMe2)2]Cl2}, where R=H, R%=Me (14), or
2
R=Me, R%=H (15). The hafnium analogue of 14
namely [Hf(h-C5H4CMe2PMe2)2Cl2] (16) was prepared
in a similar manner (see Scheme 3). In a typical prepa-
ration a stirred THF solution of ZrCl4(THF)2 at 0 °C
was added dropwise to a THF solution of compound 2.
The compound [Zr(h-C5Me4CH2PMe2)2Cl2] (15) was
isolated as a pale-yellow air-sensitive microcrystalline
solid, soluble in dichloromethane, pyridine and THF.
Treatment of the dichloro derivative [Zr(h-
C5H4CMe2PMe2)2Cl2] (14) with methyllithium gives the
corresponding dimethyl derivative [Zr(h-C5H4CMe2-
PMe2)2Me2] (17).
Treatment of 15 in toluene with two equivalents of
the Lewis acid [B(C6F5)3] gave a pale-yellow solution,
the NMR spectra of which may be assigned to the
Fig. 2. Molecular structure of 13.
Table 3
stoichiometry
{[Zr(h-C5Me4CH2PMe2)2]Cl}{(C6F5)3-
,
Selected bond lengths (A) and bond angles (°) for 13
BClB(C6F5)3} (18). The 11B{1H}-NMR spectrum of 18
displays a single peak at l −13.0. The value for the
11B{1H}-NMR spectrum of the [ClB(C6F5)3]− anions is
around l −3.0 [19a], while the value of l −13.0
resembles more closely the resonance found for
[MeB(C6F5)3]− [19a]. Given that two equivalents of
[B(C6F5)3] were used in the reaction and there is a single
11B signal, we tentatively propose the presence of the
anion [(C6F5)3BꢀClꢀB(C6F5)3]− in 18. By analogy with
the structure determined for the compound [Zr(h5,kP-
C5H4CR2PAr2)2Cl][ClB(C6F5)3]2 [19a] we tentatively
propose that 18 has the structure shown in Scheme 3.
Compound 15 in THF was added to [Pt(COD)I2] to
give a yellow powder [Zr{(h-C5Me4CH2PMe2)2Cl2}PtI2]
(19) in 45% yield. Compound 19 is poorly soluble in
common solvents and decomposed on exposure to air.
Bond lengths
Fe(1)ꢀC(3)
P(11)ꢀO(14)
P(11)ꢀC(13)
C(10)ꢀP(11)
C(1)ꢀC(2)
2.042(6)
1.450(5)
1.760(7)
1.792(6)
1.488(8)
Bond angles
C(1)ꢀFe(1)ꢀC(3)
C(9)ꢀC(10)ꢀP(11)
O(14)ꢀP(11)ꢀC(10)
C(2)ꢀC(1)ꢀFe(1)
C(3)ꢀC(1)ꢀC(2)
174.8(3)
113.3(4)
115.6(3)
129.5(4)
126.9(6)
spectively; in 11, where the effect is likely to be larger,
it is 110.49(14)°, about 1.5 and 2.8° more acute,
respectively.
Fig. 3. Molecular structure of 11.

R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
101
Table 4
and coworkers [3] have reported that the compounds
[Zr(h-C5H4CMe2PAr2)2Cl2] (Ar=phenyl, p-tolyl) can
act as chelating diphosphine ligands.
,
Selected bond lengths (A) and bond angles (°) for 11
Bond lengths
Fe(1)ꢀC(1)
C(5)ꢀC(6)
C(6)ꢀP(12)
P(12)ꢀC(14)
A THF solution of compound 2 was added to man-
ganese dichloride (MnCl2) at −78 °C to give the com-
pound [Mn(h-C5Me4CH2PMe2)2] (20) as cubic,
red–orange crystals which decomposed. The 31P-NMR
spectrum showed a singlet due to the tertiary phosphine
group at l −210.0, which is a relatively high-field
chemical shift. However, compound 20 is not diamag-
netic. The 1H-NMR spectrum of 20 exhibits the ex-
pected number of signals with appropriate integrals.
The signal at l 4.96 can be assigned to the phos-
phinodimethyl hydrogens, with further signals at l
−2.51, −4.21 and −11.29 assigned to the two pairs
of C5-methyl groups and to the backbone CH2 hydro-
gens, respectively.
The crystal structure of 20 has been determined and
the molecular structure is shown in Fig. 4. The h-cy-
clopentadienyl rings adopt a parallel, staggered confor-
mation such that the pendant dimethylphosphino-
methyl groups are as far away from each other as
possible. The view afforded by Fig. 4b demonstrates
that both PMe2 groups point up and away from the
manganese centre so as to minimise steric interaction.
2.046(2)
1.503(3)
1.904(2)
1.838(3)
Bond angles
C(16)ꢀFe(1)ꢀC(2)
C(6)ꢀC(5)ꢀFe(1)
C(5)ꢀC(6)ꢀP(12)
C(14)ꢀP(12)ꢀC(6)
163.57(10)
130.60(14)
110.49(14)
102.70(10)
The 31P-NMR spectrum shows a band at l −12.0
which shows sidebands assignable to 195Pt satellites
(JP–Pt=2304 Hz). This suggests that both the tertiary
phosphine groups are coordinated to the platinum nu-
cleus. Supporting the formulation of 19 as a bimetallic
complex is the positive mode fast atom bombardment
(FAB) mass spectrum which displays a signal at m/z
747 with the correct isotope pattern for the [M+−2I]
fragment. The magnitude of JP–Pt corresponds to trans-
arrangement of phosphine groups around the platinum
centre given that the cis-isomers are normally of the
magnitude of 3500 Hz [25,30,31]. We note that Erker
Scheme 3. (i) In THF at −78 °C, add [PtI2(COD)], 30%. (ii) In Et2O at 0 °C, add MeLi, 32%. (iii) In toluene-d8, add two equivalents [B(C6F5)3].

102
R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
Table 6
Comparison between MnꢀC bond lengths in structurally character-
ised manganocenes and their electronic spin state
Compound
Selected MnꢀC
Spin state
Reference
bond lengths a (A)
,
[Mn(h-C5Me5)2]
[Mn(h-Ci5Pr4H)2]
[Mn(h-C5Me4H)2]
[Mn(h-MeC5H4)2]
2.105(2)
2.450(5)
–
2.114(12) and
2.433(8)
2.380(6)
2.131(3)
–
–
–
2E2g
6A1g
2E2g
[37]
[38]
[39]
2E2gl6A1g [40]
[Mn(h-C5H5)2]
6A1g
2E2g
6A1g
2E2g
[40]
[40]
[41]
[41]
[Mn(h-Ci5Pr3H2)2]
[Mn(h-Ct5Bu3H2)2]
[Mn(h-Ci5PrMe4)2]
[Mn(h-Ci5Pr3Me2)2]
2E2gl6A1g [41]
a For [Mn(h-C5Me4CH2PMe2)2], MnꢀC-ring=2.092(2)–2.127(2)
,
A.
function of temperature has been determined using the
Evans’ NMR method [42,43]. An effective magnetic
moment (298 K) of 2.64 BM was found. This value is
higher than that expected for a system with one un-
paired electron (1.73 BM) [41]. Thus, compound 20 has
a predominantly low-spin character as suggested by the
similarity of bond length data to those of [Mn(h-
C5Me5)2], but also contains a contribution from the
Fig. 4. Molecular structure of 20: (a) view along the Cp–Mn–Cp
axis; (b) a side-on view.
Selected MnꢀCring bond lengths and angles for 20 are
listed in Table 5. The MnꢀC distances found for 20
broadly agree with the MnꢀC bond lengths found for
low-spin [Mn(h-C5Me5)2], with values in the range of
,
2.092(2)–2.127(2) A (see Table 6). Taken on their own,
these bond length data could suggest that 20 has a
2
low-spin, E2g character.
Substituted manganocene complexes exhibit several
electronic states and spin equilibria [32–41]. The mag-
netic susceptibility of 20 in a toluene solution as a
Table 5
,
Selected bond lengths (A) and bond angles (°) for 20
Bond lengths
MnꢀC(1)
MnꢀC(3)
MnꢀC(5)
MnꢀC(7)
MnꢀC(9)
MnꢀCcentroid
2.099(2)
2.120(2)
2.127(2)
2.105(2)
2.092(2)
1.725
Bond angles
C(1)ꢀMnꢀC(1)
C(1)ꢀC(7)ꢀC(9)
CcentroidꢀMnꢀCcentroid
180.0
107.9(2)
180.0
Fig. 5. (a) Variation of effective magnetic moment of 20 in toluene
with temperature. (b) Variation of magnetic susceptibility  of 20 in
toluene with temperature.

R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
103
6
high-spin A1g configuration. Fig. 5a shows the plot of
J=276 Hz indicative of a 3JP–Pb or 4JP–Pb coupling and
these are about one tenth the size of direct lead–phos-
phorus couplings found in tertiary phosphine–lead
complexes [44]. This suggests the P atom is not directly
bonded to the lead centre. An HMQC 2D-correlation
experiment was carried out in order to assist in the
effective magnetic moment (veff) versus temperature
(T). The graph shows a slight decrease in veff with
increasing temperature levelling off at around 2.5 BM.
In addition, a plot of magnetic susceptibility versus
temperature, shown in Fig. 5b, exhibits behaviour typi-
cal of a normal paramagnetic species where 81/T
[41].
Treatment of 20 with two equivalents of the Lewis
acid [B(C6F5)3] gave the compound [Mn{h-C5Me4CH2-
PMe2B(C6F5)3}2] (21) as an orange powder in quantita-
tive yield. This compound is relatively stable in air but
poorly soluble in common solvents. The low solubility
of the complex precluded solution NMR studies and
the sole characterising data for 21 is the microanalysis
and the FAB mass spectrum. The latter shows a peak at
m/z 1469 with the correct isotope pattern, which corre-
sponds to the molecular ion [M+]. Further signals at
m/z 957 and 445 are attributable to fragments. The new
manganocenes are shown in Scheme 4.
Addition of compound 20 in THF to [Pt(COD)I2]
gave an orange powder in 45% yield. The microanalysis
corresponds to the formulation [Mn(h-C5Me4CH2-
PMe2)2PtI2]n (22). Compound 22 appears relatively sta-
ble in air but insoluble in all common solvents. The
evidence does not permit distinction between a mono-
(n=1) or poly-molecular (n=2 or more) structure for
compound 22.
1
assignment of the 13C- and H-NMR spectra.
The tin compound [Sn(h-C5H4CMe2PMe2)2] (24) was
prepared in a similar manner to 23 and was isolated as
a fine yellow powder, in 70% yield. The compound 24
at room temperature decomposes in the light both in
the solid state and in pentane solution. The 31P{1H}-
NMR spectrum of 24 is diagnostic of the formation of
a stannocene given that the signal at l −21.4 is
accompanied by 119Sn and 117Sn satellites (I=1/2, 8.58
and 7.61% abundance, respectively). Resolution of the
two sets of satellites was not possible. The coupling-
3
value, 3JP–Sn=111 Hz, is similar with other JP–Sn
values reported [44–47]. An HMQC 2D-correlation
1
spectrum assisted the assignment of the 13C- and H-
NMR spectra. The 119Sn{1H}-NMR spectrum of 24 in
toluene-d8 at 298 K shows a binomial triplet at l
−2163 (3JSn–P=110 Hz) referenced to SnMe4 (l 0),
which compares favourably with the chemical shifts
recorded for other metallocenes of Sn(II) [45,48–51].
3
The coupling value for JSn–P is consistent with that
found in the 31P{1H}-NMR spectrum and confirms that
the pendant tertiary phosphine groups are not directly
attached to the Sn(II) centre.
In the absence of light, a mixture of PbCl2 and
[Li(C5H4CMe2PMe2)] in THF was stirred at −78 °C
to give orange microcrystals of stoichiometry corre-
sponding to [Pb(h-C5H4CMe2PMe2)2] (23) in 78% yield.
Compound 23 is moderately stable towards light in the
solid state but solutions in pentane show signs of
decomposition within a few minutes.
Addition of a [B(C6F5)3] solution in toluene to 23
gave a compound with a stoichiometry corresponding
to [Pb{h-C5H4CMe2PMe2B(C6F5)3}2] (25) as a yellow
powder, in quantitative yield. It decomposes in air and
is soluble in polar solvents. The 1H- and 13C-NMR
spectra of 25 in pyridine-d5, are similar to that obtained
for the parent plumbocene. The 31P{1H}-NMR spec-
trum displays a singlet at l −11, which is a downfield
The 31P{1H}-NMR spectrum shows coupling to the
207Pb nuclei (I=1/2, 22.6% abundance) with a value of
Scheme 4. (i) Anhydrous MnCl2 in THF at −78 °C, 66%. (ii) [B(C6F5)3] in toluene at room temperature, for 12 h, 63%.

104
R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
shift of approximately 5 ppm from that of the parent
complex 23. In addition, the three-bond P–Pb coupling
is no longer evident. This is likely to be a result of the
interaction between the 11B nucleus and the P-group.
The 11B{1H} spectrum displays a doublet at l 0.65
(JB–P=70.5 Hz) typical of a neutral, tetracoordinate
boron species which is well within the realms of PR3–
borane coupling constants [52,53].
spectrum (THF-d8, 298 K) showed two peaks indicating
that some ligand dissociation may be occurring or both
cis- and trans-isomers may be present.
Treatment of [PtI2(COD)] in THF with 24 in THF at
room temperature gave an orange compound with a
stoichiometry corresponding to [Sn(h-C5H4CMe2-
PMe2)2PtI2]n (28) in 60% yield. Low solubility pre-
cluded NMR studies.
The compound [PtI2(COD)] in THF was treated with
compound 23 in THF at room temperature giving an
air-sensitive orange powder of stoichiometry [Pb(h-
C5H4CMe2PMe2)2PtI2]n (26), in 50% yield. Compound
26 is an air-sensitive orange solid, which is sparingly
soluble in THF. The FAB mass spectrum (NOBA
matrix) of compound 26 contains two peaks and al-
though the signal due to the molecular ion (m/z=990)
is not present, signals at m/z=863 [M−I] and m/z=
736 [M−2I] with the correct isotope patterns are ob-
served. Complex 26 exhibits a 31P{1H}-NMR resonance
at l −4.7, which is shifted upfield by about 11 ppm
from the parent compound 23 and the 195Pt isotope
(I=1/2, 33.7% relative abundance) accounts for a split-
ting due to the 31P–195Pt coupling. The data do not
allow distinction between a monomolecular bimetallic
structure and a bi- or poly-nuclear structure (see
Scheme 5). Oligomeric structures of similar compounds
have been reported by Graham and Erker [3,17,26,54].
Addition of [Pd(COD)Cl2] in THF to 23 gave yel-
low–orange [Pb(h-C5H4CMe2PMe2)2PdCl2]n (27) which
is only sparingly soluble in THF. The 31P{1H}-NMR
Treatment of the rhodium ethylene chloride dimer
[Rh(C2H4)2Cl]2 with one equivalent of [Li(C5Me4CH2-
PMe2)] (1) gave [Rh(h,kP-C5Me4CH2PMe2)(C2H4)]
(29) that was isolated as a dark yellow solid in 40%
yield. The 31P-NMR spectrum in benzene-d6 shows a
doublet at l −29.6 (JRh–P=198.4 Hz). Complex 29
was oxidised with iodine leading to a brown microcrys-
talline product [Rh(h,kP-C5Me4CH2PMe2)I2] (30). The
31P resonance appears as a doublet at l −25.2 with
J
Rh–P=136.6 Hz. The reaction of the ligand precursor
1 with the iridium cyclooctene chloride dimer [Ir(-
COE)2Cl]2 gave a dark brown solid and this was treated
with one equivalent of iodine. [Ir(h,kP-C5Me4CH2-
PMe2)I2] (31) was obtained in 38% yield as a brown
microcrystalline solid. The 31P resonance of complex 31
in CD2Cl2 is observed at l −27.5. The structures
proposed for 29–31 are shown in Scheme 6.
The rhodium and iridium derivatives described above
are not stable for long periods in solution. After two
days very shielded resonances appear in the 31P-NMR
spectra at l −166 and −160 for the solutions of 30
and 31, respectively. Simultaneously, the 1H-NMR
Scheme 5. (i) M=Pb: [PdCl2(COD)] in THF at room temperature, for 12 h, 32%. (ii) [B(C6F5)3] in toluene at room temperature, for 12 h, 50%.
(iii) [PtI2(COD)] in THF at room temperature, for 12 h, 36% (26) and 32% (28).

R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
105
Scheme 6. (i) [Rh(C2H4)2Cl]2 in THF at 0 °C, for 6 h, 40%. (ii) For M=Rh (30): [Rh(C2H4)2Cl]2 in THF at 0 °C, for 6 h; then I2 in toluene
at room temperature, for 4 h, 52%. For M=Ir (31): [Ir(COE)2Cl]2 in THF at 0 °C, for 8 h; then I2 in toluene at room temperature, for 4 h, 43%.
spectra show the broadening of all the signals and the
appearance of new resonances in the range l 1.3–2.0.
trogen or by purging with dinitrogen for ca. 15 min
prior to use. Solvents and solutions were transferred,
using a positive pressure of nitrogen, through stainless-
steel cannulae (diameter 0.5–2.0 mm) and mixtures
were filtered in a similar way using modified cannulae
which could be fitted with glass-fibre filter discs (What-
man GF/C). Deuterated NMR solvents (Aldrich, Goss
Scientific) were refluxed and distilled from potassium
metal (benzene-d6, toluene-d8, THF-d8), from CaH2
(CD2Cl2 and pyridine-d5) or from MgSO4 (acetone-d6),
distilled, degassed by the freeze–pump–thaw technique
prior to use and stored in Young’s ampoules under
argon. D2O was degassed by purging with argon for
approximately 15 min prior to use. NMR solvents were
transferred using a teat pipette in an inert atmosphere
dry box, or by vacuum distillation using an all-glass
apparatus.
The compounds MnCl2, TiCl4, NH4PF6, KN-
(SiMe3)2, NaN(SiMe3)2, ZnMe2 (2.0 M solution in hex-
anes), LitBu (1.7 M solution in pentane), LinBu (2.5 M
solution in light petroleum ether (b.p. 40–60 °C)),
LiMe (1.6 M solution in Et2O), HCl (1.0 M solution in
Et2O), naphthalene (C8H10) and CH3I, were purchased
from Aldrich Chemical Company and used without
further purification. 1,2,3,4-Tetramethylcyclopent-2-
enone was purchased from Aldrich and distilled before
use. ZrCl4 and HfCl4 were purchased from Aldrich and
sublimed prior to use. LiN(SiMe3)2 was purchased from
Aldrich and was recrystallised from THF before use.
3. Experimental
All manipulations of air- and/or moisture-sensitive
materials were performed under an inert atmosphere of
pure argon or dry dinitrogen using standard Schlenk
line techniques or in an inert atmosphere dry box
containing dinitrogen. Inert gases were purified firstly
by passage through columns filled with activated molec-
,
ular sieves (4 A) and then either manganese(II) oxide
suspended on vermiculite, for the Schlenk line, or
BASF catalyst, for the dry box. Celite® filtration aid
was purchased from Fluka Chemie and oven-dried at
150 °C prior to use. Filtrations were generally per-
formed using modified stainless steel cannulae, which
had been fitted with glass fibre filter discs. All glassware
and cannulae were dried overnight at 150 °C before
use.
,
Solvents were pre-dried over activated 4 A molecular
sieves and then distilled from Na–K alloy (light
petroleum ether (b.p. 40–60 °C), Et2O, pentane and
DME), from Na (petroleum ether (b.p. 100–120 °C)
and toluene), from K (THF), P2O5 (MeOH) or from
CaH2 (CH2Cl2), under a slow continuous stream of
dinitrogen. Glassware was thoroughly degassed by the
pump–fill technique followed by re-admission of dini-

106
R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
Trimethylphosphine (PMe3) [55], ZrCl4(THF)2 and
HfCl4(THF)2 [56], tetramethyl dithiodiphosphane [57a],
dimethylphosphine [57b], tetramethylcyclopentenone
[58–61], 1,2,3,4-tetramethylfulvene [61], 6,6-dimethyl-
fulvene and 6,6-pentamethylenefulvene [62], [Rh-
(C2H4)2Cl]2 [63] and [Ir(COE)2Cl]2 [64], were prepared
as described.
Solution NMR spectra were recorded using either a
Varian Mercury 300 (1H 300 MHz, 13C 75.5 MHz, 19F
282.3 MHz, 31P 121.6 MHz, 119Sn 111.9 MHz and 207Pb
62.7 MHz) or a Varian UNITYplus (1H 500 MHz, 11B
160.4 MHz, 13C 125.7 MHz, 31P 202.4 MHz) spectrom-
eter and are at room temperature (r.t.) unless otherwise
stated. The spectra were referenced internally relative to
the residual protio-solvent (1H) and solvent (13C) reso-
nances relative to Me4Si (1H, 13C, l=0) or externally
to BF3·Et2O (11B, l=0); 85% H3PO3 (31P, l=0);
SnMe4 (119Sn, l=0); PbOAc4 (207Pb, l= −2675) or
CFCl3 (19F, l=0). Chemical shifts (l) are expressed in
ppm and coupling constants (J) in Hz.
obtained as a pyrophoric, white powder. Yield: 0.60 g
(74%).
3.2. Synthesis of [Na(C5Me4CH2PMe2)] (2)
To a THF (25 ml) solution of 8 (1.34 g, 6.2 mmol) at
−78 °C was added via a cannula, a THF solution (25
ml) of NaN(SiMe3)2 (1.05 g, 6.2 mmol). The solution
was allowed to warm to r.t. and stirred for 12 h. The
solvent was removed under reduced pressure from the
resulting yellow solution. The off-white product was
washed with pentane (2×10 ml) and isolated by filtra-
tion. After the residual solvent was removed under
reduced pressure compound 2 was obtained as a py-
rophoric, white powder. Yield: 1.19 g, (87%).
3.3. Synthesis of [K(C5Me4CH2PMe2)] (3)
To a THF solution (25 ml) of 8 (1.00 g, 5.1 mmol) at
−78 °C was added via a cannula, a THF solution (25
ml) of KN(SiMe3)2 (1.03 g, 5.1 mmol). The solution
was allowed to warm to r.t. and stirred for 12 h. The
solvent was removed under reduced pressure from the
resulting yellow solution. The off-white product was
washed with pentane (2×10 ml) and isolated by filtra-
tion. After the residual solvent was removed under
reduced pressure compound 3 was obtained as a py-
rophoric, white powder. Yield: 0.95 g, (79%).
Electrospray mass spectra were recorded using a
Micromass LC TOF electrospray ionisation mass spec-
trometer. FAB mass spectrometry was performed by
the EPSRC Mass Spectrometry Service at Swansea.
Elemental analyses were performed by the Microanalyt-
ical Department of the Inorganic Chemistry Labora-
tory, Oxford.
3.1. Synthesis of [Li(C5Me4CH2PMe2)] (1)
3.4. Synthesis of [Li(C5H4CMe2PMe2)] (4)
3.1.1. Method A
1,2,3,4-Tetramethylfulvene (1.4 g, 10.45 mmol) in
THF (50 ml) was added to LiPMe2·0.22Et2O, (1.02 g,
10.45 mmol) in THF (50 ml) stirred with a glass
encased magnetic stir bar at −78 °C. The red solution
of the fulvene instantly changes colour upon contact
with the other reagent. The solution was allowed to
warm gradually to r.t. overnight. The solvent was re-
moved under vacuum and the pale green product
washed with three portions of Et2O and thoroughly
dried in vacuo, to yield 1.4g (64%) of a white py-
rophoric solid, which was shown to have no THF
coordinated to it by NMR spectroscopy. On scaling up,
the same reaction product needed recrystallising from
THF.
To a stirred solution of LiPMe2·0.22Et2O (3.58 g, 43
mmol) in THF (40 ml) at −78 °C was added dropwise
a THF solution of 6,6-dimethylfulvene (5.42 g, 51
mmol) and the reaction mixture left to stir overnight
after slowly warming to r.t. The solvent was then
removed from the yellow solution under reduced pres-
sure affording a sticky yellow solid. The product was
triturated and then washed with pentane (3×15 ml)
and filtration of the supernatant followed by removal of
residual volatiles under reduced pressure yielded the
compound [Li(C5H4CMe2PMe2)] (4) as a fine, white
powder. Yield: 4.7g (63%).
3.5. Synthesis of [Li{C5H4C(CH2)5PMe2}] (5)
3.1.2. Method B
To a stirred THF solution (25 ml) of [HC5Me4CH2-
PMe2] (8) (0.80 g, 4.0 mmol) at −78 °C was added via
a cannula, a THF solution (25 ml) of LiN(SiMe3)2 (0.63
g, 4.1 mmol). The solution was allowed to warm to r.t.
and stirred for 12 h. The solvent was removed under
reduced pressure from the resulting yellow solution.
The off-white product was washed with pentane (2×10
ml) and isolated by filtration. After the residual solvent
was removed under reduced pressure compound 1 was
The compound LiPMe2·0.22Et2O (100 mg, 1.2 mmol)
was suspended in THF and cooled to −78 °C. A
solution of 6,6-pentamethylenefulvene (176 mg, 1.2
mmol) in THF was slowly added with stirring. The
resulting pale yellow solution was allowed to warm to
r.t. overnight. All volatiles were removed in vacuo to
yield a very sticky yellow material. Washing with a
pentane–Et2O mixture and trituration converts this
into a free-flowing white powder. Yield: 40%.

R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
107
3.6. Synthesis of [HC5Me4CH2PMe2H][Cl] (6)
combined organic fractions were dried under vacuum
leaving a very air sensitive, pale yellow oil. Yield: 79%.
To a yellow solution of LiCH2PMe2 (3.12 g, 38
mmol) in THF (125 ml) at −78 °C was added drop-
wise via a cannula, a THF solution (75 ml) of te-
tramethylcyclopent-2-enone (5.25 g, 38 mmol). The
resulting yellow solution was allowed to warm to r.t.
and was stirred for a further 12 h. Upon further cooling
to −78 °C, a 1.0 M solution of HCl in Et2O (79.8 ml,
2.1 equivalents) was added over 2.5 h and formation of
a white precipitate ensued. The mixture was then stirred
for 2 h and the white solid isolated on a glass frit after
transfer via a wide bore Teflon cannula. The product
was washed with THF (2×20 ml) and pentane (2×30
ml) before residual solvent was removed under reduced
pressure to yield compound 6 as a white powder. Crude
yield: 7.2 g (80%).
3.9. Synthesis of [Fe(p-C5Me4CH2PMe2)2] (9)
The salt 1 (1.0 g, 5 mmol) and anhydrous FeCl2 (320
mg, 2.5 mmol) were placed in a Schlenk vessel and
THF was added at −78 °C. The mixture was allowed
to warm to r.t. overnight to give a dark brown solution.
The solvent was removed in vacuo and the brown
residue was extracted three times with pentane. Con-
centration and crystallisation at −78 °C yielded or-
ange blocks. Yield: 45–49%. The product, occasionally
contaminated with a dark, tarry substance, could be
further purified by vacuum sublimation, filtration
through silica gel or further recrystallisation. Crystals
of 9 suitable for X-ray diffraction were grown by
dissolving a small amount in ca. 2 ml of benzene and
allowing the solvent to slowly evaporate under a very
slow stream of nitrogen gas.
3.7. Synthesis of [HC5Me4CH2PMe2H][PF6] (7)
To a pale yellow solution of 6 (12.19 g, 52 mmol) in
degassed H2O (50 ml) at r.t. was added via cannula a
solution of NH4PF6 (10.24 g, 57 mmol) in degassed
H2O (50 ml) with the immediate precipitation of a
white solid. The product was transferred to a glass frit
and filtered then washed with degassed H2O (2×30
ml). Residual water was removed from the resulting
white solid under reduced pressure to yield compound 7
as a white powder. Yield: 15.1 g (85%).
3.10. Synthesis of [Fe(p-C5H4CMe2PMe2)2] (10)
A solution of 4 (280 mg, 1.6 mmol) in THF was
treated with anhydrous FeCl2 (100 mg, 0.8 mmol) in
THF at −78 °C. The orange coloured reaction mix-
ture was left to stir for 3 h during which time it was
allowed to warm to r.t. All volatiles were then removed
under vacuum and the residue extracted with pentane
to yield an orange crystalline solid. Yield: 130 mg
(21%).
3.8. Synthesis of [HC5Me4CH2PMe2] (8)
3.8.1. Method A
3.11. Synthesis of [Fe{p-C5H4C(CH2)5PMe2}2] (11)
To a suspension of 7 (13.81 g, 40 mmol) in MeOH
(50 ml) was added a solution of KOH (2.25 g, 40 mmol)
in MeOH (20 ml). The suspension changed to a cloudy
solution with the concomitant evolution of a phosphine
odour. Pentane (50 ml) was added to the solution,
which was stirred for 10 min. On separation of the two
layers, the top pentane layer was transferred via a
cannula into a Schlenk vessel containing MgSO4 (3.0 g)
and the suspension stirred. The suspension was then
filtered into a clean Schlenk vessel to yield a colourless
solution from which solvent was removed under re-
duced pressure. Compound 8 was isolated as a very
pale yellow oil. Yield: 3.50 g (45%).
A solution of [LiC5H4C(CH2)5PMe2] (5) in THF was
made up by treating 6,6-pentamethylenefulvene (350
mg, 2.4 mmol) with LiPMe2·0.22Et2O (200 mg, 2.4
mmol). Anhydrous FeCl2 (1.2 mmol, 150 mg, half an
equivalent) was suspended in THF and added as a
slurry to the solution of the lithium salt. The yellow
solution turned cloudy with FeCl2 crystals, and the
reaction could be monitored by the dissolution of the
particulates and concomitant formation of an orange
tint. After 3 h the reaction was deemed to be complete
and all volatiles were removed under vacuum, the
residue extracted with pentane and then dried under
vacuum. Analytically pure crystals could be grown by
crystallisation at −20 °C in a minimum amount of
Et2O. Yield: 100 mg first crop, 50 mg second crop (10%
first crop, 5% second crop).
3.8.2. Method B
The compound [HC5Me4CH2PMe2H][PF6], (7) (170
mg, 0.5 mmol) was suspended in degassed water (50 ml)
and KOH (100 mg, 1.7 mmol) was added. The liquid
was stirred under nitrogen for 10 min, and then pentane
(20 ml) was added with stirring. The two phases were
allowed to separate and then the organic layer was
carefully decanted into another flask via a cannula.
This process was repeated three times, and then the
3.12. Synthesis of [Fe(p-C5H4CMe2PMe3)2I2] (12)
A pentane solution of 10 (40 mg, 0.1 mmol) was
treated with a large excess of MeI (0.5 ml, ca. 1.5
mmol) and the mixture was stirred for 5 h. A flocculent

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R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
pale yellow precipitate formed, which was found to be
the title compound, in almost quantitative yield. Re-
crystallisation from MeOH at −78 °C yielded analyti-
cally pure microcrystals of 12.
was filtered through Celite. The filtrate was concen-
trated and cooled to −80 °C. Yield: 170 mg (30%).
3.17. Synthesis of [Zr(p-C5H4CMe2PMe2)2Me2] (17)
3.13. Synthesis of [Fe(p-C5Me4CH2P(O)Me2)2] (13)
A suspension of 15 (992 mg, 2 mmol) in Et2O was
treated with LiMe (1.4 M in Et2O, 2.86 ml, 4 mmol) at
−78 °C and allowed to warm to r.t. The resulting
yellow suspension was filtered through Celite and
washed through with Et2O. All volatiles were removed
under vacuum and the residue was washed with a small
amount of petroleum ether (b.p. 40–60 °C). Yield: 300
mg (32%).
A sample of 9 in benzene-d6 in an NMR tube was
opened to air and left to evaporate for 2 days. Orange
crystals of the bisphosphine oxide derivative 13 were
formed, and they were found to be suitable for an
X-ray structural investigation.
3.14. Synthesis of [Zr(p-C5H4CMe2PMe2)2Cl2] (14)
3.18. Synthesis of {[Zr(p-C5Me4CH2PMe2)2]Cl}-
{(C6F5)3BClB(C6F5)3} (18)
Compound 4 (1.74 g, 10 mmol) and ZrCl4 (1.16 g, 5
mmol) were suspended in toluene in two separate
Schlenk vessels. The suspension of the lithium salt was
added to the other at −78 °C with stirring and al-
lowed to warm overnight to r.t. A light brown floccu-
lent solid formed with a red supernatant solution. The
solvent was removed in vacuo, the residue was ex-
tracted with CH2Cl2 until the solution was colourless
and filtered through Celite to remove any suspended
LiCl. A pale yellow solid formed which could be
purified by overnight recrystallisation at −20 °C from
CH2Cl2 to yield 1.25 g (2.53 mmol, 50%) of the desired
product. Note that the product is not stable for long
periods in CH2Cl2.
To a Young’s tap NMR tube was added a toluene-d8
solution of compound 15 (10.0 mg, 0.018 mmol) and
two equivalents of B(C6F5)3 (18.5 mg, 0.036 mmol).
This compound was characterised by NMR only.
3.19. Synthesis of [Zr(p-C5Me4CH2PMe2)2Cl2PtI2] (19)
To a Schlenk vessel containing stirred THF (25 ml)
at −78 °C were simultaneously added dropwise via
two cannulae, solutions of 15 (100 mg, 0.18 mmol) and
PtI2(COD) (105 mg,0.18 mmol) in THF (25 ml each)
over 30 min. The resulting orange solution was stirred
at r.t. for 1 h after which time a pale orange precipitate
began to form. The solution was filtered and solvent
was removed under reduced pressure. The resulting
red–orange solid was triturated with pentane (10 ml),
solvent was removed under reduced pressure and com-
pound 19 was isolated as an orange solid. Yield: 53 mg
(30%).
3.15. Synthesis of [Zr(p-C5Me4CH2PMe2)2Cl2] (15)
To a stirred THF solution (25 ml) of ZrCl4(THF)2
(259 mg, 0.69 mmol) at 0 °C was added dropwise a
solution of 2 (306 mg, 1.40 mmol) in THF (20 ml). The
colour changed from pale yellow to orange before
reverting to yellow again on warming to r.t. The yellow
solution was then stirred for 12 h. The solvent was
removed under reduced pressure and the yellow solid
triturated with pentane (2×10 ml) then extracted into
dichloromethane (2×20 ml). The solvent was removed
from the resulting yellow solution under reduced pres-
sure to yield compound 15 as pale yellow microcrystals.
Yield: 267 mg (70%).
3.20. Synthesis of [Mn(p-C5Me4CH2PMe2)2] (20)
To a stirred solution of 2 (1.0 g, 4.6 mmol) in THF
(30 ml) at −78 °C was added via a solid addition
Schlenk vessel, MnCl2 (289 mg, 2.3 mmol). The mixture
was slowly warmed to 40 °C using a water bath and
maintained at that temperature for 1 h. The resulting
orange solution was stirred for a further 12 h, cooling
slowly to r.t. Solvent was removed under reduced pres-
sure and the oily, orange product triturated with pen-
tane (30 ml). The orange product was then extracted
into pentane (3×30 ml) and filtered via a cannula into
a Schlenk vessel. The solvent was removed under re-
duced pressure to leave a concentrated solution (20 ml)
which was cooled to 4 °C for 2 days. Compound 20
was isolated as orange, cubic, X-ray quality crystals.
Yield: 0.68 g (66%).
3.16. Synthesis of [Hf(p-C5H4CMe2PMe2)2Cl2] (16)
The lithium salt
4 (350 mg, 2 mmol) and
HfCl4(THF)2 (465 mg, 1 mmol) were each loaded into
separate Schlenk vessels and suspended in cold (−
78 °C) THF. The suspension of the lithium salt was
then added to the other with stirring and allowed to
warm to r.t. overnight. The resulting yellow–green
solution was pumped down under vacuum, and the
residue taken up in CH2Cl2. The resulting suspension

R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
109
3.21. Synthesis of [Mn{p-C5Me4CH2PMe2B(C6F5)3}2]
(21)
sure. Compound 24 was isolated as a waxy, yellow solid
and stored at −40 °C in the dark. Yield: 650 mg
(91%).
To a stirred solution of 20 (98 mg, 0.22 mmol) in
toluene (50 ml) at r.t. was added via a cannula, a
toluene solution (25 ml) of B(C6F5)3 (225 mg, 0.44
mmol). The orange solution was stirred for a further 12
h. The solvent was removed from the resulting yellow
suspension under reduced pressure and the solid, pale
orange–yellow product washed with pentane (30 ml)
and residual volatiles were removed under reduced
pressure. The compound 21 was isolated as a yellow
solid. Yield: 203 mg (63%).
3.25. Synthesis of [Pb{p-C5H4CMe2PMe2B(C6F5)3}2]
(25)
A solution of [B(C6F5)3] (95 mg, 0.18 mmol) in
toluene (25 ml) was added dropwise to a solution of 23
(50 mg, 0.09 mmol) in toluene (25 ml) at r.t. The
resulting yellow solution was stirred for 72 h. The
solvent was removed under reduced pressure from the
yellow solution and the resulting yellow solid washed
with pentane (2×20 ml). Final removal of volatiles
under reduced pressure yielded compound 25 as a
yellow powder. Yield: 70 mg (50%).
3.22. Synthesis of [Mn(p-C5Me4CH2PMe2)2PtI2] (22)
To a solution of [PtI2(COD)] (131 mg, 0.22 mmol) in
THF (25 ml) at r.t. was added a THF solution of 20
(100 mg, 0.22 mmol) over 60 min. The orange–red
mixture was stirred for 2 h after which the solution was
filtered and solvent was removed under reduced pres-
sure. The resulting red–orange solid was triturated with
pentane (10 ml), remaining volatiles were removed un-
der reduced pressure and the compound 22 was isolated
as a red–orange solid. Yield: 86 mg (44%). Microanaly-
sis results for a compound with the empirical formula
C24H40I2MnP2Pt (MW=894.36 amu): Found: C, 32.7;
H, 4.5; P, 6.8. Calc.: C, 32.2; H, 4.8; P, 6.9%.
3.26. Synthesis of [Pb(p-C5H4CMe2PMe2)2PtI2]n (26)
A yellow solution of [PtI2(COD)] (83 mg, 0.14 mmol)
in THF (30 ml) was slowly added to a solution of 23
(77 mg, 0.14 mmol) in THF (20 ml) at r.t. The resulting
yellow solution was stirred for 12 h. Volatiles were
removed under reduced pressure from the yellow–or-
ange solution and the yellow solid washed with pentane
(2×20 ml). Removal of residual pentane under reduced
pressure yielded compound 26 as an orange powder.
Yield: 50 mg (36%).
3.23. Synthesis of [Pb(p-C5H4CMe2PMe2)2] (23)
3.27. Synthesis of [Pb(p-C5H4CMe2PMe2)2PdCl2]n (27)
To a foil-covered Schlenk vessel containing a mixture
of PbCl2 (300 mg, 1.1mmol) and 4 (368 mg, 2.2 mmol)
was added THF (30 ml) at −78 °C. The resulting
yellow suspension was stirred for 12 h. The orange
solution containing a white precipitate was filtered via a
cannula to yield a dark yellow solution from which the
solvent was removed under reduced pressure. An or-
ange, oily solid resulted. The product was triturated
with pentane (10 ml) and the solid then extracted into
pentane and stored at −40 °C overnight. Compound
23 was isolated as a microcrystalline, orange solid.
Yield: 400 mg (68%).
A yellow solution of [PdCl2(COD)] (52 mg, 0.18
mmol) in THF (30 ml) was slowly (10 min) added to an
orange solution of 23 (100 mg, 0.18 mmol) in THF (20
ml) at r.t. The resulting orange solution was stirred for
12 h. The solvent was removed under reduced pressure
from the yellow–orange solution and the yellow solid
washed with pentane (2×10 ml). Removal of residual
pentane under reduced pressure yielded compound 27
as an orange–yellow powder. Yield: 40 mg (32%).
Microanalysis results for a compound with the empiri-
cal formula C20H32Cl2PbP2Pd (MW=718.9 amu):
Found: C, 33.4; H, 4.5. Calc.: C, 33.4; H, 4.5%.
31P{1H}-NMR spectrum (pyridine-d5): l −3.4 (s),
−5.7 (s).
3.24. Synthesis of [Sn(p-C5H4CMe2PMe2)2] (24)
To a foil-covered Schlenk vessel containing a mixture
of SnCl2 (300 mg, 1.6 mmol) and 4 (555 mg, 3.2 mmol)
was added THF (20 ml) at −78 °C. The resulting
yellow suspension was stirred for 12 h. The dark yellow
solution containing a white precipitate was filtered via a
cannula to yield a yellow solution from which the
solvent was removed under reduced pressure. A yellow,
waxy solid was isolated. The product was triturated
with pentane (10 ml) and the solid then extracted into
pentane and the solvent removed under reduced pres-
3.28. Synthesis of [Sn(p-C5H4CMe2PMe2)2PtI2]n (28)
A yellow solution of [PtI2(COD)] (103 mg, 0.18
mmol) in THF (30 ml) was slowly (10 min) added to an
orange solution of 24 (80 mg, 0.18 mmol) in THF (20
ml) at r.t. The resulting orange solution was stirred for
12 h. The solvent was removed under reduced pressure
from the yellow–orange solution and the yellow solid
washed with pentane (2×10 ml). Removal of residual
pentane under reduced pressure yielded compound 28

110
R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
as an insoluble orange–yellow powder. Yield: 40 mg
(32%). Microanalysis results for a compound with the
empirical formula C20H32I2SnP2Pt (MW=902.01 amu):
Found: C, 26.7; H, 3.6. Calc.: C, 26.6; H, 3.6%.
dryness. The residue was extracted in Et2O and filtered.
A solution of I2 (254 mg, 1.0 mmol) in toluene was
added to the previous solution and the resulting mix-
ture was stirred for 4 h. The solvent was evaporated to
dryness and a tiny amount of I2 sublimed. The residue
was re-extracted in toluene and the solution was filtered
through a small column (ca. 2 cm height) of neutral
alumina. The resulting orange–brown solution was col-
lected, concentrated and layered with pentane. Cooling
to −80 °C afforded brown microcrystals of 30. Yield:
287 mg (52%).
3.29. Synthesis of [Rh(p,sP-C5Me4CH2PMe2)(C2H4)]
(29)
A THF solution of the ligand precursor 1 (202 mg,
1.0 mmol) was slowly added at 0 °C to a solution of
[Rh(C2H4)2Cl]2 (195 mg, 0.5 mmol) in the same solvent.
The solution darkened immediately and a white precip-
itate formed. The mixture was stirred at r.t. for 6 h and
the solvent was then evaporated to dryness. The brown
residue obtained was extracted in Et2O to give an
orange–brown solution that was filtered and evapo-
rated to dryness. The slightly oily product formed was
frozen in liquid N2 and scratched with a spatula leading
to a brown powder on heating to r.t. The product was
dissolved in pentane and the solution filtered through
neutral alumina (grade I, 2 cm height column). A
yellow–brown crystalline solid formed when the solu-
tion was concentrated and cooled at −80 °C. Yield:
130 mg (40%).
3.31. Synthesis of [Ir(p,sP-C5Me4CH2PMe2)I2] (31)
Treatment of a THF solution of [Ir(COE)2Cl]2 (448
mg, 0.5 mmol) with a solution of 1 (202 mg, 1.0 mmol)
in THF at 0 °C led to the formation of a white
precipitate and a brown solution. The mixture was
reacted for 8 h at r.t. and the solvent was then evapo-
rated to dryness. The residue was extracted in Et2O and
the solution was filtered and evaporated to dryness. The
brown powder obtained was weighed (413 mg, 0.83
mmol) and redissolved in toluene. A toluene solution of
I2 (210 mg, 0.83 mmol) was added dropwise at r.t. and
the mixture stirred for 4 h. The solvent was removed in
vacuum and a small excess of I2 sublimed out. The
brown solid was redissolved in toluene and filtered
through a column of neutral alumina (ca. 2 cm height).
The solution was concentrated, layered with pentane
and cooled to −80 °C overnight. Brown crystals of 31
formed. Yield: 275 mg (43%).
3.30. Synthesis of [Rh(p,sP-C5Me4CH2PMe2)I2] (30)
The first part of this synthesis was similar to that
described for 29: a solution of 1 (202 mg, 1.0 mmol)
and [Rh(C2H4)2Cl]2 (195 mg, 0.5 mmol) in THF was
reacted for 6 h and the solvent was evaporated to
Table 7
Crystal data and structure refinement parameters
9
13
11
20
Empirical formula
Temperature (K)
Crystal system
C24H40FeP2
150
Monoclinic
C2/c
C
150
Monoclinic
C2/c
24H40FeO2P2
C26H40FeP2
150
Orthorhombic
Pna21
C24H40MnP2
150
Monoclinic
P21/c
Space group
Crystal description
Unit cell dimensions
Yellow prism
Yellow–green prism
Orange block
Orange block
,
a (A)
11.624(2)
21.254(4)
9.811(2)
90
96.78(3)
90
11.263(2)
20.969(4)
10.172(2)
90
98.05(3)
90
25.257(5)
6.4030(13)
14.588(3)
90
90
90
8.653(1)
16.202(1)
8.610(1)
90
97.945(3)
90
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
Z
4
4
4
4
Crystal size (mm)
Data measured
Unique data
Rint
Refinement on
Parameters refined
R (all data)
0.3×0.3×0.5
4583
2428
0.020
F
123
0.2×0.3×0.6
2302
2302
0.3×0.3×0.3
4059
2519
0.2×0.2×0.3
2449
2449
0
0.031
0
F2
F2
F2
138
0.1027
0.1781
266
0.0196
0.0520
131
0.0594
0.0957
0.0472
0.0415
Rw (all data)

R.M. Bellabarba et al. / Journal of Organometallic Chemistry 640 (2001) 93–112
111
Noltemeyer, A. de Meijere, H. Butenschon, Chem. Commun.
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3.32. X-ray crystallography
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Crystals were isolated under N2, covered with pe-
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,
0.71069 A). Structure solution was performed using the
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refinement was performed using the CRYSTALS package
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