Preparation and coordination chemistry of Ph2PNHNHpy

Article abstract of DOI:10.1016/S0277-5387(03)00115-3

Ph₂PNHNHpy (1) can be oxidised to form Ph₂P(E)NHNHpy (E = O, S, Se, 2-4) or reacted with appropriate metal complexes such as [PtCl₂(cod)], [PtMe₂(cod)], [Pd(μCl)(η³-C₃H₅)]₂, [RhCl(cod)]₂, [RuCl₂(η³:η³-C₁₀ H₁₆)]₂, [RuCl₂(P-Cy)]₂, [IrCp*Cl₂]₂, and [Cu(MeCN)₄][PF₆] to give a range of new monodentate complexes. All new compounds have been charactersised by elemental analyses, NMR, IR and mass spec. The X-ray structures of Ph₂PNHNHpy, Ph₂P(Se)NHNHpy [RuCl₂(η³:η³C₁₀ H₁₆)(Ph₂PNHNHpy-P)] and [IrCp*Cl₂(Ph₂PNHNHpy-P)] are reported. Apart from monodentate P coordination all of the structures contain hydrazine based NH hydrogen bonding.

Full text of DOI:10.1016/S0277-5387(03)00115-3

Polyhedron 22 (2003) 1397Á1405
/
www.elsevier.com/locate/poly
Preparation and coordination chemistry of Ph2PNHNHpy
Alexandra M.Z. Slawin, Joanne Wheatley, Matthew V. Wheatley, J. Derek Woollins *
School of Chemistry, University of St. Andrews, St. Andrews, Fife, KY16 9ST, UK
Received 6 January 2003; accepted 24 February 2003
Abstract
Ph2PNHNHpy (1) can be oxidised to form Ph2P(E)NHNHpy (Eꢀ
/
O, S, Se, 2Á4) or reacted with appropriate metal complexes
/
such as [PtCl2(cod)], [PtMe2(cod)], [Pd(mCl)(h3-C3H5)]2, [RhCl(cod)]2, [RuCl2(h3:h3-C10H16)]2, [RuCl2(p-Cy)]2, [IrCp*Cl2]2, and
[Cu(MeCN)4][PF6] to give a range of new monodentate complexes. All new compounds have been charactersised by elemental
analyses, NMR, IR and mass spec. The X-ray structures of Ph2PNHNHpy, Ph2P(Se)NHNHpy [RuCl2(h3:h3-
C10H16)(Ph2PNHNHpy-P)] and [IrCp*Cl2(Ph2PNHNHpy-P)] are reported. Apart from monodentate P coordination all of the
structures contain hydrazine based NH hydrogen bonding.
# 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Hydrazine; Hydrogen; Bonding; Structures
1. Introduction
Relatively few examples of amino containing pyridyl-
phosphine ligands are known despite the relative ease of
Hemilabile phosphines are of interest in both homo-
genous catalysis and coordination chemistry [1]. Phos-
formation of phosphorusÁ
/
nitrogen bonds compared to
phosphorusÁcarbon bonds. Examples include 2-(diphe-
/
nylphosphinoamino)pyridine [27], 2-(phenylphosphino)-
bisaminopyridine [27] and 2-(trisaminopyridyl)phos-
phine [27]. We have recently reported studies on 2-
(diphenylphosphinoamino)pyridine [27] and demon-
strated that it display three, possibly four different
coordination modes. Katti et al. [28,29] reported the
inclusion of phosphorus donors within the hydrazine
ligand to develop new ligand systems. These ligands
phorusÁnitrogen containing ligands have particular use
in catalysis where it is necessary for part of the ligand to
dissociate to allow an organic fragment to coordinate
/
and undergo transformation. The presence of PÃ
/N
bidentate ligands enables many different and important
catalytic processes to occur including asymmetric hy-
droboration [2], carbonylation of alkynes [3], Stille
coupling [4] and asymmetric hydrogenation of highly
substituted alkenes [5] to name a few. Some of these
processes have had pyridyl phosphines such as 2-
(diphenylphosphino)pyridine applied to them success-
fully [6]. Properties of this ligand have been extensively
studied [1,6,7] together with related ligands containing
organic spacer units which have been developed to
increase the distance between the phosphorus and
pyridyl nitrogen donor sites and these include
possess either NÃ
/
NÃ
/
PÃ
/
NÃ
/
N or PÃ
/
NÃ
/
NÃ/P backbones.
In this work, we report the preparation of a new
phosphine which has a hydrazine backbone and the
potential to act as a hemilable ligand. Illustrative
coordination complexes have been prepared.
2. Experimental
Ph2PCH(R)py (where Rꢀ
/
H [8Á/10], CH2OEt [11,12],
or PPh2 [13Á17]) and Ph2PCH2CH2py [18Á
/
/26].
2.1. General
Unless otherwise stated, all reactions were carried out
under an oxygen-free nitrogen atmosphere using stan-
dard Schlenk techniques. Diethyl ether and thf were
purified by reflux over sodium-benzophenone and dis-
* Corresponding author. Tel.: ꢁ
463384.
E-mail address: jdw3@st-and.ac.uk (J.D. Woollins).
/
44-1334-463861; fax: ꢁ44-1334-
/
0277-5387/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0277-5387(03)00115-3

1398
A.M.Z. Slawin et al. / Polyhedron 22 (2003) 1397Á1405
/
tillation under nitrogen. Dichloromethane was heated to
reflux over calcium hydride and distilled under nitrogen.
Toluene and hexane were heated to reflux over sodium
and distilled under nitrogen. The complexes [MCl2(cod)]
2.4. Ph2P(Se)NHNHpy (4)
Elemental selenium (40 mg, 0.5 mmol) and
Ph2PNHNHpy (150 mg, 0.5 mmol) were dissolved
together under nitrogen in dry toluene (10 cm3). The
reaction mixture was heated for 4 h, and then most of
the solvent was removed under reduced pressure. The
remaining mixture was placed in the fridge overnight
and a white powder precipitated from the solution,
which was isolated by filtration. Yield 119 mg, 63%.
Microanalysis: Found (calculated for C17H16N3PSe) C
55.16 (54.85), H 4.18 (4.33), N 10.98 (11.29). dp (CDCl3)
(Mꢀ
[PtMeX(cod)] (Xꢀ
/
Pt
or
Pd;
codꢀcycloocta-1,5-diene),
/
/
Cl or Me), [Pd(mCl)(h3-C3H5)]2,
[RhCl(cod)]2, [RuCl2(h3:h3-C10H16)]2, [RuCl2(p-Cy)]2,
[IrCp*Cl2]2, and [Cu(MeCN)4][PF6] and Ph2PNHNHpy
1 were prepared as described previously [27,30]. Infra-
red spectra were recorded as KBr discs in the range
4000Á
/
200 cmꢂ1 on a PerkinÁ
Elmer 2000 FTIR/RA-
/
MAN spectrometer. NMR spectra were recorded on a
Gemini 2000 spectrometer (operating at 121.4 MHz for
31P and 300 MHz for 1H). Microanalyses were per-
formed by the St. Andrews University service and mass
spectra by the Swansea Mass Spectrometer Service.
61 ppm 1J{31PÃ
aromatic), 7.4Á7.5 (m, 8H, aromatic), 6.8 (d, 1H,
aromatic), 6.65 (t, 1H, aromatic), 6.5 (br s, 1H,
/
77Se} 768 Hz. dH 7.9Á
8.1 (m, 4H,
/
/
2
NH[py]), 5.0 (d, 1H, J{31PÃ
/
1H} 19 Hz, NH[P]). IR
(KBr) cmꢂ1 nNH 3255, nNH 3076, nCN[py] 1601, nPN 992,
nPSe 587. Mass spec (EIꢁ): 373(Mꢁ) (Scheme 1).
2.2. Ph2P(O)NHNHpy (2)
2.5. [PtCl2(Ph2PNHNHpy)2-P] (5)
Ph2PNHNHpy (300 mg, 1 mmol) was dissolved in thf
(20 cm3). H2O2 (35 mg, 1 mmol) was added dropwise
over 5 min to give a colourless solution. The reaction
mixture was stirred at room temperature for 1 h before
removing all the solvent on the vacuum line. The solid
formed was dissolved in CH2Cl2 before reducing the
volume to 0.5 cm3 on the vacuum line. Diethyl ether (2
cm3) was added to precipitate the product, which was
isolated by filtration. Yield 203 mg, 64%. Microanalysis:
Found (calculated for C17H16N3OP) C 65.56 (66.01), H
5.42 (5.21), N 13.15 (13.59). dp (CDCl3) 26.9 ppm. dH
A CH2Cl2 (5 cm3) solution of [Pt(cod)Cl2] (64 mg, 0.1
mmol) was added dropwise to a CH2Cl2 (5 cm3) solution
of Ph2PNHNHpy (100 mg, 0.3 mmol). The resulting
solution was stirred for a few hours before, the white
solid that formed on stirring, being isolated by filtration.
Yield 104 mg, 72%. Microanalysis: Found (calculated
for C34H32N6P2Cl2Pt) C 48.30 (47.90), H 3.15 (3.78), N
1
9.88 (9.86). dp (CDCl3) 44.0 ppm J{31PÃ
/
195Pt} 3855
7.55 (m,
16H, aromatic), 6.8 (d, 2H, aromatic), 6.65 (t, 2H,
Hz. dH (CDCl3) 7.9Á
/
8.1 (m, 8H, aromatic), 7.4Á
/
aromatic), 6.4 (br s, 2H, NH[py]), 5.0 (d, 2H,
1H} 19 Hz, NH[P]). IR (KBr) cmꢂ1 nNH 3143,
2J{31PÃ
/
(CDCl3) 8.1 (m, 5H, aromatic), 7.2Á
/
7.7 (m, 9H,
1H}
aromatic), 6.7 (m, 1H, NH), 6.1 (d, 1H, 1J{1HÃ
/
nCN[py] 1600, nPN 997, nPtCl 307, nPtCl 288. Mass spec
(NOBA Matrix): 817(Mꢂ
Clꢂ), 780(Mꢂ2Clꢂ).
21 Hz, NH). IR (KBr) cmꢂ1 nNH 3344, nNH 3076, nCN[py]
1595, nPO 1312, nPN 997. Mass spec (EIꢁ): 309(Mꢁ).
/
/
2.6. [PtMe2(Ph2PNHNHpy-P)2-P] (6)
Ph2PNHNHpy (150 mg, 0.5 mmol) and [PtMe2(cod)]
(85 mg, 0.5 mmol) were dissolved together in CH2Cl2 (7
cm3) under nitrogen and stirred for 5 min. Excess
2.3. Ph2P(S)NHNHpy (3)
Elemental sulfur (219 mg, 0.7 mmol) and
Ph2PNHNHpy (2 g, 0.7 mmol) were dissolved together
under nitrogen in dry toluene (18 cm3). The reaction
mixture was sonicated to ensure that the entire solid was
dissolved before heating with a heat gun. The reaction
mixture was left to cool overnight with stirring, which
precipitated out a solid that was isolated by filtration.
Yield 1.9 g, 85%. Microanalysis: Found (calculated for
C17H16N3PS) C 62.91 (62.75), H 4.67 (4.96), N 13.12
(12.92). dp (CDCl3) 63.8 ppm. dH (CDCl3) 7.9Á
4H, aromatic), 7.4Á7.55 (m, 8H, aromatic), 6.8 (d, 1H,
aromatic), 6.65 (t, 1H, aromatic), 6.4 (br s, 1H, NH[py]),
/
8.1 (m,
/
2
5.0 (d, 1H, J{31PÃ
nNH 3276, nNH 3090, nCN[py] 1602, nPN 991, nPS 648. Mass
spec (NOBA Marix): 348(Mꢁ
Na), 325(Mꢁ).
/
1H} 19 Hz, NH[P]). IR (KBr) cmꢂ1
Scheme 1. Formation of Ph2PNHNHpy and Ph2P(E)NHNHpy
/
ligands (EꢀO, S, Se).
/

A.M.Z. Slawin et al. / Polyhedron 22 (2003) 1397Á
/
1405
1399
hexane was added, then most of the solvent removed
under reduced pressure. The solid formed was subse-
quently isolated by filtration. Yield 54 mg, 13%.
Microanalysis: Found (calculated for C36H38N6P2Pt) C
1J{31PÃ
pyC[6]H), 7.1Á
aromatic), 6.5 (t, 1H, aromatic), 6.1 (s, 1H, NH[py]),
/
103Rh} 156 Hz. dH (CDCl3) 7.9 (d, 1H,
/7.6 (m, 12H, aromatic), 6.7 (d, 1H,
4.5 (d, 1H, J{31PÃ
/
1H} 12 Hz, NH[P]), 4.0 (br s, 4H,
2
53.66 (53.27), H 5.29 (4.72), N 9.90 (10.35). dp (CDCl3)
71.2 ppm J{31PÃ
3341, nNH 3051, nCN[py] 1598, nPN 985.
C8H12), 2.3 (m, 4H, C8H12), 1.7 (m, 4H, C8H12). IR
(KBr) cmꢂ1 nNH 3206, nCN[py] 1597, nPN 996, nRhCl 250.
1
/
195Pt} 1984 Hz. IR (KBr) cmꢂ1 nNH
Mass spec (NOBA Matrix): 540(Mꢁ
/
H), 504 (Mꢂ
Clꢂ).
/
2.7. [PtMeCl (Ph2PNHNHpy)2-P] (7)
2.10. [RuCl2(h3:h3-C10H16)Ph2PNHNHpy-P] (10)
Ph2PNHNHpy (87 mg, 0.3 mmol) and [PtMeCl(cod)]
(50 mg, 0.1 mmol) were dissolved under nitrogen in dry
toluene (10 cm3). The resulting solution was stirred
vigorously for a few hours yielding a white precipitate
that was isolated by filtration. Yield 98 mg, 40%.
Microanalysis: Found (calculated for C35H35N6P2ClPt)
Ph2PNHNHpy (50 mg, 0.1 mmol) and [RuCl2(h3:h3-
C10H16)]2 (52 mg, 0.08 mmol) were dissolved under
nitrogen in dry toluene (10 cm3). The resulting solution
was stirred for an hour before reducing the solvent
volume to 2 cm3. Diethyl ether was added to form a
precipitate, which redissolved on the addition of excess
ether. The solvent was reduced before hexane was added
drop wise to form an orange/yellow precipitate that was
then isolated by filtration. Yield 43 mg, 42%. Micro-
analysis: Found (calculated for C27H32N3PCl2Ru) C
54.51 (53.90), H 5.42 (5.37), N 6.98 (6.99). dp (CDCl3)
C 51.61 (50.52), H 3.87 (4.24), N 10.17 (10.10). dp
(CDCl3) 60.4 ppm J{31PÃ
1
/
195Pt} 3183 Hz. dH (CDCl3)
7.8Á
/
8.1 (m, 9H, aromatic), 7.2Á7.6 (m, 16H, aromatic),
/
6.7 (m, 5H, NH and aromatic), 6.3 (s, 2H, NH), 0.0 (s,
2
3H, J{195PtÃ
3251, nNH 3224, nCN[py] 1600, nPN 997, nPtCl 266. Mass
spec (NOBA Matrix): 796(Mꢂ
Clꢂ).
/
1H} 829 Hz, CH3). IR (KBr) cmꢂ1 nNH
69.5 ppm. dH (CDCl3) 7.9Á
/
8.1 (m, 4H, aromatic), 7.4Á
/
/
7.55 (m, 8H, aromatic), 6.8 (d, 1H, aromatic), 6.65 (t,
1H, aromatic), 6.4 (br s, 1H, NH[py]), 5.0 (d, 1H,
2.8. [PdCl(h3-C3H5)(Ph2PNHNHpy-P)] (8)
2J{31PÃ
2H, J{1HÃ
2H, J{1HÃ
/
1H} 19 Hz, NH[P]), 5.2 (br m, 2H, CHc), 4.3 (d,
/
31P} 8.8 Hz, CHa), 3.4 (m, 2H, CHb), 3.2 (d,
A CH2Cl2 (10 cm3) solution of Ph2PNHNHpy (113
mg, 0.39 mmol, 2 equiv.) was added dropwise by use of a
syringe pump to a CH2Cl2 (3 cm3) solution of [Pd(m-
Cl)(h3-C3H5)]2 (71 mg, 0.195 mmol) under nitrogen over
2.5 h with stirring. The solvent volume was removed
under pressure before excess hexane was added to
precipitate a beige solid after cooling overnight then
isolated by filtration. Yield 92 mg, 50%. Microanalysis:
Found (calculated for C21H21ClN3PPd) C 50.28 (50.44),
H 4.37 (4.44), N 8.28 (8.82). dp (CDCl3) 66.4 ppm. dH
(CDCl3) 7.9 (m, 4H, aromatic), 7.7 (d, 1H, aromatic),
7.4 (m, 6H, aromatic), 7.1 (t, 1H, aromatic), 6.7 (d, 1H,
aromatic), 6.5 (t, 1H, aromatic), 6.1 (s, 1H, NH[py]), 5.5
/
31P} 3.3 Hz, CH), 2.7 (m, 2H, CH2), 2.2 (s,
6H, CH3). IR (KBr) cmꢂ1 nNH 3279, nCN[py] 1596, nPN
984, nRuCl 305, nRuCl 245. Mass spec (NOBA Matrix):
624(Mꢁ
/
Na), 602(MꢁH).
/
2.11. [RuCl2(p-Cy)Ph2PNHNHpy-P] (11)
Ph2PNHNHpy (200 mg, 0.7 mmol) and [Ru(p-
Cy)Cl2]2 were dissolved under nitrogen in dry CH2Cl2
(10 cm3). The resulting red/orange solution was stirred
for 15 min before the solvent was reduced to 2 cm3.
Hexane was added to precipitate an orange solid that
was isolated by filtration. Yield 330 mg, 81%. Micro-
analysis: Found (calculated for C27H30N3PCl2Ru) C
54.17 (54.08), H 4.21 (5.05), N 6.96 (7.01). dp (CDCl3)
72.7 ppm. dH (CDCl3) 7.9 (m, 4H, aromatic), 7.7 (d, 1H,
aromatic), 7.4 (m, 6H, aromatic), 7.1 (t, 1H, aromatic),
6.7 (d, 1H, aromatic), 6.5 (t, 1H, aromatic), 6.1 (s, 1H,
(d, 1H, 2J{31PÃ
22 Hz, CH2), 4.7 (t, 1H, J{1HÃ
2H, J{1HÃ1H} 24 Hz, CH2). IR (KBr) cmꢂ1 nNH 3202,
nNH 3051, nCN[py] 1601, nPN 997, nPdCl 285. Mass spec
(NOBA Matrix): 440(Mꢂ
Clꢂ).
/
1H} 8 Hz, NH[P]), 5.4 (t, 2H, J{1HÃ
/
1H}
/
1H} 14 Hz, CH), 3.7 (t,
/
/
NH[py]), 5.4 (d, 1H, 2J{31PÃ
/
1H} 12 Hz, NH[P]), 5.3 (d,
1H} 6
2.9. [Rh(C8H12)Cl Ph2PNHNHpy-P] (9)
2H, 1J{1H-1H} 2 Hz, cymene), 5.2 (d, 2H, 1J{1HÃ
/
Hz, cymene), 2.5 (m, 1H, ArCH), 1.9 (s, 3H, ArCH3),
0.9 (d, 6H, ArCH3). IR (KBr) cmꢂ1 nNH 3332, nNH
3296, nCN[py] 1597, nPN 987, nRuCl 294. Mass spec
A toluene (5 cm3) solution of [Rh(cod)Cl]2 (84 mg, 0.2
mmol) was added dropwise to a toluene solution of
Ph2PNHNHpy (100 mg, 0.3 mmol) under nitrogen. The
resulting solution was stirred for 10 min before the
solvent volume was reduced and hexane added to
precipitate a brown solid that was isolated by filtration.
Yield 126 mg, 68%. Microanalysis: Found (calculated
(NOBA Matrix): 622(Mꢁ
/
Na), 600(Mꢁ
/
H), 564(Mꢂ
/
Clꢂ), 528(Mꢂ2Clꢂ).
/
2.12. [IrCp*Cl2(Ph2PNHNHpy-P)] (12)
for C25H28PClN3Rh×
/
(CH2Cl2)0.5) C 52.51 (52.50), H
A CH2Cl2 (10 cm3) solution of Ph2PNHNHpy (78
mg, 0.26 mmol) was added dropwise by a syringe pump
4.57 (5.02), N 7.90 (7.22). dp (CDCl3) 71.0 ppm, d,

1400
A.M.Z. Slawin et al. / Polyhedron 22 (2003) 1397Á1405
/
to a CH2Cl2 (3 cm3) solution of [Cp*IrCl2]2 (105 mg,
0.13 mmol) under nitrogen over 2 h with stirring. The
solvent was reduced under pressure before excess hexane
was added to precipitate an orange solid after cooling
overnight that was isolated by filtration. Yield 157 mg,
nitrogen in dry CH2Cl2 (10 cm3). The resulting dark
orange solution was stirred for 20 min before removing
the solvent on the vacuum line. Dry hexane (2 cm3) was
added to precipitate a dark brown solid, which was
isolated by filtration. Yield 310 mg, 80%. Microanalysis:
Found (calculated for C27H30N3PSCl2Ru) C 50.88
(51.34), H 4.41 (4.79), N 6.46 (6.66). dp (CDCl3) 81.1
ppm. IR (KBr) cmꢂ1 nNH 3448, nNH 3178, nCN[py] 1611,
86%.
Microanalysis:
Found
(calculated
for
C27H33Cl2N3Pir) C 46.60 (46.75), H 4.45 (4.80), N 5.74
(6.06). dp (CDCl3) 45.0 ppm. dH (CDCl3) 7.9 (m, 4H,
aromatic), 7.8 (d, 1H, aromatic), 7.4 (m, 6H, aromatic),
7.15 (t, 1H, aromatic), 6.6 (d, 1H, aromatic), 6.4 (t, 1H,
nPN 995, nPS 635. Mass spec (NOBA Matrix): 559(Mꢂ
/
Cl2).
aromatic), 6.05 (s, br, 1H, NH), 5.8 (d, 1H, J{31PÃ
/
1H}
33.1 Hz, NH[P]), 1.4 (d, 15H). IR (KBr) cmꢂ1 nNH
3318, nNH 3057, nCN[py] 1598, nPN 987, nIrCl 285. Mass
2.16. [Cu (Ph2P(S)NHNHpy-S,N)2][PF6] (16)
spec (NOBA Matrix): 692(Mꢁ), 656(Mꢂ
/
Clꢂ),
Ph2P(S)NHNHpy (200 mg, 0.6 mmol) and
[Cu(MeCN)4][PF6] (115 mg, 0.3 mmol) were dissolved
together under nitrogen in dry CH2Cl2 (20 cm3). The
resulting dark green solution was stirred for 2 h before
the volume of solvent present was reduced to about 2
cm3. Dry diethyl ether (15 cm3) was added to yield a
precipitate that was isolated by filtration to yield a
green/blue solid. Yield 204 mg, 77%. Microanalysis:
Found (calculated for C34H32P3N6S2F6Cu) C 47.30
(47.55), H 3.66 (3.76), N 9.70 (9.79). dp (CDCl3) 65.9
619(Mꢂ
/
2Clꢂ).
2.13. [Cu (Ph2PNHNHpy-P,N)2][PF6] (13)
Ph2PNHNHpy (200 mg, 0.6 mmol) and
[Cu(MeCN)4][PF6] (127 mg, 0.3 mmol) were dissolved
under nitrogen in dry CH2Cl2 (5 cm3). The resulting
solution was stirred for about 10 min before the solvent
volume was reduced on the vacuum line to 2 cm3. Dry
diethyl ether (8 cm3) was added to yield a creamy white
precipitate, which was isolated by filtration and washed
with excess ether then dried on the vacuum line. Yield
193 mg, 71%. Microanalysis: Found (calculated for
C34H32N6P3F6Cu) C 51.04 (51.36), H 4.05 (4.06), N
10.86 (10.57). IR (KBr) cmꢂ1 nNH 3291, nCN[py] 1614,
ppm. dH (CD2Cl2) 7.9Á
/
8.1 (m, 8H, aromatic), 7.4Á7.55
/
(m, 16H, aromatic), 6.8 (d, 2H, aromatic), 6.65 (t, 2H,
2
aromatic), 5.0 (d, 2H, J{31PÃ
(KBr) cmꢂ1 nNH 3262, nCN[py] 1611, nPN 997, nPS 622.
Mass spec (NOBA Matrix): 713(Mꢂ
PF6ꢂ).
/
1H} 19 Hz, NH[P]). IR
/
nPN 999. Mass spec (NOBA Matrix): 649(Mꢂ
/
PF6ꢂ).
2.17. Crystallography
2.14. [Rh(C8H12) Ph2P(S)NHNHpy-S,N][Cl] (14)
X-ray diffraction studies were performed at 293 K
using a Rigaku AFC7S with Cu Ka radiation [com-
pound 1] or a Bruker SMART diffractometer with
graphite-monochromated Mo Ka radiation. The struc-
tures were solved by direct methods, non-hydrogen
atoms were refined with anisotropic displacement para-
meters; hydrogen atoms bound to carbon were idealised,
the NH protons were located by a DF map. Structural
refinements were by the full-matrix least-squares
method on F [compound 1, TeXsan [31]] or F2 using
SHELXTL [32]. Details of the data collections are
summarised in Table 1.
Ph2P(S)NHNHpy (200 mg, 0.6 mmol) was dissolved
under nitrogen in dry toluene (8 cm3). [Rh(cod)Cl]2 (152
mg, 0.3 mmol) was dissolved in dry toluene (5 cm3)
under nitrogen. The rhodium complex solution was
added drop wise over about 10 min with stirring. The
reaction mixture was then stirred for 20 min at room
temperature, to yield a yellow precipitate that was
isolated by filtration, washed with ether and dried on
the vacuum line. Yield 274 mg, 79%. Microanalysis:
Found (calculated for C25H30N3PSRhCl) C 53.08
(52.50), H 4.73 (4.93), N 7.28 (7.35). dp (CDCl3) 64.3
ppm. dH (CDCl3) 7.9Á
/
8.1 (m, 4H, aromatic), 7.4Á7.55
/
(m, 8H, aromatic), 6.8 (d, 1H, aromatic), 6.65 (t, 1H,
aromatic), 6.4 (br s, 1H, NH[py]), 5.0 (d, 1H,
3. Results and discussion
2J{31PÃ
/
1H} 19 Hz, NH[P]), 4.0 (br s, 4H, C8H12), 2.3
Reaction of 2-hydrazinopyridine with 1 equiv. of
Ph2PCl in the presence of NEt3, proceeds in thf to give
1 which was isolated (50% yield) by filtration from the
Et3NHꢁClꢂ as a white crystalline solid upon recrys-
tallisation from chloroform. The 31P{1H} NMR spec-
trum of 1 consists of a singlet at dp 49.6 ppm. In the IR
spectrum two bands are observed at 3313 and 3200
cmꢂ1 which are assigned to the two nNH vibrations
whilst the nCN[py] and nPN vibrations are observed at
(m, 4H, C8H12), 1.7 (m, 4H, C8H12). IR (KBr) cmꢂ1
nNH 3163, nCN[py] 1611, nPN 998, nPS 640. Mass spec
(NOBA Matrix): 536(Mꢂ
Clꢂ).
/
2.15. [Ru (p-Cy)Ph2P(S)NHNHpy-S,N][Cl2] (15)
Ph2P(S)NHNHpy (200 mg, 0.6 mmol) and [RuCl2(p-
Cy)]2 (188 mg, 0.3 mmol) were dissolved together under

A.M.Z. Slawin et al. / Polyhedron 22 (2003) 1397Á
/
1405
1401
Table 1
Details of the X-ray data collections and refinements
1
4
10
12
Empirical formula
M
C
17H16N3P
C17H16N3PSe
372.26
C28H33Cl5N3PRu
720.86
triclinic
C27H31Cl2IrN3P
691.62
triclinic
293.31
monoclinic
P21/c
Crystal system
Space group
monoclinic
P21/c
¯
¯
P1
P/
1
/
˚
a (A)
5.592(4)
17.947(6)
15.139(3)
90
15.7931(19)
11.8898(14)
9.3268(11)
90
8.9712(2)
13.5564(7)
13.6359(7)
106.947(2)
103.608(2)
93.094(3)
1528.36(12)
2
13.2992(3)
14.4656(3)
16.7774(4)
71.7020(10)
83.7060(10)
64.4440(10)
2763.38(11)
4
˚
b (A)
˚
c (A)
a (8)
b (8)
97.81(3)
90
98.024(3)
90
g (8)
3
U (A )
˚
1505.3(9)
4
1.579
1734.2(4)
4
2.257
Z
m (mmꢂ1
)
1.026
7628
4303
5.103
13884
7819
Reflections measured
Independent reflections
2605
2339
7237
2439
Final R1, wR2[Iꢀ
/
2s(I)]
0.070, 0.057
0.0553, 0.1283
0.0676, 0.1129
0.0269, 0.0460
1602 and 989 cmꢂ1, respectively. The FAB mass
spectrum gave the expected parent ion and fragmenta-
tion pattern and microanalysis gave satisfactory results.
resonances (CDCl3) at dP 26.9 and 63.8 ppm for the
oxide and the sulfide, respectively. The selenide analo-
gue exhibits a single 31P{1H} NMR resonance (CDCl3)
at dP 61.0 ppm with selenium satellites 1J(31PÃ
/
77Se) 768
In the solid state structure (Fig. 1) the N(14)Ã
/
C(13)Ã
/
Hz which is typical for a PÄ
/
Se group (Table 2). In the
solid state the sulfur and selenide analogues are iso-
N(2)Ã
/
N(1) backbone of this ligand is almost planar,
˚
with the phosphorus being above this plane by 1.65 A. 1
forms an infinite chain of hydrogen bonded dimer pairs
morphous; the Se compound 4 is reported since this
behaved better crystallographically. The PÃ
is significantly shorter than that in 1. The N(14)Ã
N(2)ÃN(1) backbone is planar, and the phosphorus is
not as far out of plane in 4 [1.18 A] as is the case in 1.
The hydrogen-bonding motif observed here is consider-
ably different to that of 1. There are two types of H
/
N bond in 4
in the solid state, via the interaction of the hydrazine NÃ
/
/
C(13)Ã
/
H groups with the pyridyl N on adjacent molecules
˚
/
[N(14)
/
ꢀ ꢀ ꢀ
/
N(2A) separation 2.99 A, the N(14)
1.89 A, N(2)ÃH(2n)ꢀ ꢀ ꢀN(14) 159.58]. A second weaker
hydrogen bond from the other NÃH group links these
dimers together to form infinite chains [N(14B) N(1)
ꢀ ꢀ ꢀ
H(1n) distance of 2.29 A, N(1)ÃH(1n)
N(14B) of 1538].
/
ꢀ ꢀ ꢀ
/
H(2n)
˚
˚
/
/
/
/
/
/
˚
˚
bond NÃ
[N(1) N(14A) 2.94, H(1n)
ꢀ ꢀ ꢀ
ꢀ ꢀ ꢀN(14) 1638; N(2)ꢀ ꢀ ꢀSe(1B) 3.75, H(2N)
Se(1B) 1698] (Fig. 2).
/
N
/
ꢀ ꢀ ꢀ
/
N and NÃ
/
H
/
ꢀ ꢀ ꢀ
/
Se to give an infinite chain.
3.33 A, N(14B)
/
ꢀ ꢀ ꢀ
/
/
/
˚
/
/
/
ꢀ ꢀ ꢀ
/
N(14) 1.99 A, N(1)Ã
/H(1n)/
ꢀ ꢀ ꢀ
/
/
/
/
/
ꢀ ꢀ ꢀSe(1B) 2.78
/
The oxide (2) Ph2P(O)NHNHpy was easily prepared
by the addition of excess aqueous hydrogen peroxide to
1 in thf whilst the sulfur (3) and seleno (4) analogues
were prepared by the addition of elemental S or Se to the
ligand in toluene. Satisfactory microanalyses were
obtained for 3 and 4 though 2 proved difficult to purify
completely [this may be due to overoxidation] and the
EIꢁ mass spectral data gave the expected parent ion and
fragmentation patterns. 31P{1H} NMR show single
˚
A N(2)Ã
/
H(2N)
/
ꢀ ꢀ ꢀ
/
3.1. Coordination chemistry of Ph2PNHNHpy
Reaction of [PtCl2(cod)] with Ph2PNHNHpy gives
[PtCl2(Ph2PNHNHpy)2-P] (5) in good yield (72%),
however, there was no evidence of P,N chelate forma-
tion. The FAB mass spectrum of 5 contains the expected
parent ion and fragmentation pattern and the complex
displays a single resonance with platinum satellites in the
1
31P{1H} NMR spectrum (dp 44.0 ppm, J{31PÃ
/
195Pt}
3855 Hz), which indicates the presence of Clꢂ trans to
P. The IR spectrum has nNH at 3143 cmꢂ1, nCN[py] and
nPN at 1600 and 997 cmꢂ1, respectively and two nPtCl
bands at 307 and 288 cmꢂ1 which support the cis
geometry (Table 3).
Reaction of [PtMe2(cod)] with
Ph2PNHNHpy gives [PtMe2(Ph2PNHNHpy)2-P] (6)
(dp 71 ppm, 1J{31PÃ195Pt} 1985 Hz). IR spectral
analysis showed that the pyridyl N is not bound in
2
equiv. of
/
Fig. 1. The X-ray structure of Ph2PNHNHpy (1).

1402
A.M.Z. Slawin et al. / Polyhedron 22 (2003) 1397Á1405
/
Table 2
Characterisation data for Ph2PNHNHpy and its derivatives
Compound
31P{1H} NMR IR (cmꢂ1
)
Microanalysis/% Found (calc.)
dp (ppm)
nPN nNH nNH nCN[py] nMCl
C
H
N
Ph2PNHNHpy (1)
Ph2P(O)NHNHpy (2)
49.6
26.9
989 3313 3200 1602
997 3344 3076 1595
991 3276 3090 1602
992 3255 3076 1601
Á
1312
648
/
69.09 (69.60) 5.29 (5.50) 14.01 (14.33)
65.56 (66.01) 5.42 (5.21) 13.15 (13.59)
62.91 (62.75) 4.67 (4.96) 13.12 (12.92)
55.16 (54.85) 4.18 (4.33) 10.98 (11.29)
Ph2P(S)NHNHpy (3)
Ph2P(Se)NHNHpy (4) a
63.8
61.0 a
44.0 b
71.2 c
60.4 d
66.4
587
[PtCl2(Ph2PNHNHpy-P)2] (5)
[PtMe2(Ph2PnHNHpy-P)2] (6)
[PtClMe(Ph2PnHNHpy-P)2] (7)
[PdCl(h3-(C3H5) (Ph2PNHNHpy-P)] (8)
997
Á/
3143 1600
307, 288 48.30 (47.90) 3.15 (3.78) 9.88 (9.86)
985 3341 3051 1598
997 3251 3224 1600
997 3202 3051 1601
Á/
53.66 (53.27) 5.29 (4.72) 9.90 (10.35)
51.61 (50.52) 3.87 (4.24) 10.17 (10.10)
50.28 (50.44) 4.37 (4.44) 8.28 (8.82)
52.51 (52.50) 4.57 (5.02) 7.90 (7.22)
266
285
250
[Rh(C8H12)Cl(Ph2PNHNHpy-P)]×
/
(CH2Cl2)0.5 (9) 71.0 e
996 3206
984 3279
Á
Á/
/
1597
1596
[RuCl2(h3:h3-C10H16) (Ph2PNHNHpy-P)] (10)
[RuCl2(p-Cy) (Ph2PNHNHpy-P)] (11)
[IrCp*Cl2(Ph2PnHNHpy-P)] (12)
69.5
72.7
45.0
305, 245 54.51 (53.90) 5.42 (5.37) 6.98 (6.99)
987 3332 3296 1597
987 3318 3057 1598
294
285
54.17 (54.08) 4.21 (5.05) 6.96 (7.01)
46.60 (46.75) 4.45 (4.80) 5.74 (6.06)
51.04 (51.36) 4.05 (4.06) 10.86 (10.57)
53.08 (52.50) 4.73 (4.93) 7.28 (7.35)
50.88 (51.34) 4.41 (4.79) 6.46 (6.66)
47.30 (47.55) 3.66 (3.76) 9.70 (9.79)
[Cu(Ph2PNHNHpy-P,N)2][PF6] (13)
[Rh(cod)(Ph2P(S)NhNHpy-S,N)][Cl] (14)
[Ru(p-Cy)(Ph2P(S)NHNHpy-S,N][Cl2] (15)
[Cu(Ph2P(S)NhNHpy-S,N][PF6] (16)
Á/
999 3291
998
995 3448 3178 1611
Á/
1614
Á/
64.3
81.1
65.9
Á/
3168 1611
640
635
622
997
Á/
3262 1611
a
1J{31PÃ77Se} 768 Hz.
/
b
c
1J{31PÃ
/
195Pt} 3855 Hz.
1J{31PÃ
1J{31PÃ
/
195Pt} 1984 Hz.
d
e
/
195Pt} 3183 Hz.
103Rh} 156 Hz.
1J{31PÃ
/
ð1Þ
showed a single broad peak at 66.4 ppm, indicating that
the complex is fluxional. The IR spectrum was again
useful in determining the coordination of the ligand
around the Pd centre. The peak observed at 1601 cmꢂ1
indicating the pyridyl N is not bound to the metal centre
Fig. 2. The X-ray structure of Ph2P(Se)NHNHpy (4).
and the PdÃ
/
Cl stretch was observed at 280 cmꢂ1
addition of [RhCl(cod)]2
.
this complex as nCN[py] is observed at 1598 cmꢂ1
.
Upon slow
to
[PtMeCl(Ph2PNHNHpy)2-P] (7) was prepared in a
similar manner (Eq. 1). The complex was isolated by
filtration in a yield of 40% and its microanalyses gave
satisfactory results for the bis(phosphine) species
Ph2PNHNHpy, [Rh(cod)Cl(Ph2PNHNHpy-P)] (9) was
obtained in a yield of 68%. Microanalysis gave only
fairly satisfactory results though the 31P{1H} NMR
(CDCl3) displayed the expected peak at dp 71.0 ppm
103Rh} of 156 Hz.
formed. The FAB mass spectrum contains Mꢂ
Clꢂ at
/
1
with a coupling constant of J{31PÃ
/
796 whilst 31P{1H} NMR spectroscopy revealed a single
sharp resonance with platinum satellites, (dp 60.4 ppm,
FAB mass spectral analysis gave the expected parent ion
and fragmentation pattern and the IR spectrum showed
bands at 3206, 996 and 250 cmꢂ1 which are assigned as
nNH, nPN and nRhCl vibrations, respectively. The pre-
sence of the nCN[py] at 1597 cmꢂ1 was found is indicative
of a non-chelated complex. However, upon further
analysis of the NMR and IR spectra we believe that
the complex formed was fluxionally chelated due to the
1J{31PÃ
atoms are trans to each other. The IR bands observed at
/
195Pt} 3183 Hz), indicating the two phosphorus
3251, 3224, 1600, 997 and 266 cmꢂ1 represent nNH, nNH
nCN[py], nPN and nPtCl, respectively.
,
The reaction of Ph2PNHNHpy with [Pd(m-Cl)(h3-
C3H5)]2 gave the expected product [PdCl(h3-
C3H5)(Ph2PNHNHpy)2-P] (8). The 31P NMR (CDCl3)

A.M.Z. Slawin et al. / Polyhedron 22 (2003) 1397Á
/
1405
1403
Table 3
Table 4
Selected bond length (A) and angles (8) for [RuCl2(h3:h3-
C10H16)(Ph2PNHNHpy-P)] and [IrCp*Cl2(Ph2PNHNHpy-P)]
˚
˚
Selected bond lengths (A) and angles (8) for Ph2PNHNHpy and
Ph2P(Se)NHNHpy
˚
˚
Selected bond lengths (A) and angles (8)
1
4
Selected bond lengths (A) and angles (8)
10
12
Bond lenghts
Bond lengths
P(1)Ã
Se(1)Ã
N(14)Ã
/
N(1)
P(1)
C(13)
1.709(7) 1.656(5)
2.1145(15)
M(1)Ã
M(1)Ã
M(1)Ã
/
Cl(1)
Cl(2)
P(1)
2.458(3)
2.422(3)
2.432(3)
2.25
2.4009(15)
2.4284(14)
2.2928(13)
2.19
/
Á/
/
/
1.356(9) 1.332(7)
1.842(8) 1.797(5)
1.821(8) 1.814(6)
1.346(9) 1.390(7)
1.411(8) 1.410(6)
/
P(1)Ã
P(1)Ã
N(2)Ã
N(1)Ã
/C(7)
Average M(1)Ã
P(1)ÃN(1)
N(14)ÃC(13)
/
C(L)
/
C(1)
/
1.698(8)
1.352(13)
1.379(14)
1.406(11)
1.660(4)
1.355(6)
1.362(7)
1.404(5)
/
C(13)
N(2)
/
/
N(2)Ã
N(1)Ã
/
C(13)
/N(2)
Bond angles
N(1)ÃP(1)Ã
C(1)ÃP(1)ÃC(7)
N(1)ÃN(2)ÃC(13)
N(2)ÃC(13)ÃC(18)
N(1)Ã
P(1)ÃN(1)Ã
N(2)Ã
N(14)Ã
C(7)ÃP(1)Ã
N(1)ÃP(1)Ã
C(1)ÃP(1)Ã
/
/C(1)
98.5(4)
106.5(3)
Bond angles
P(1)ÃM(1)Ã
Cl(1)ÃM(1)Ã
N(1)ÃP(1)ÃM(1)
N(2)ÃN(1)ÃP(1)
N(14)Ã
C(13)ÃN(2)Ã
Cl(1)ÃM(1)Ã
/
/
100.1(4) 105.4(3)
118.9(7) 118.0(5)
125.1(8) 122.7(5)
104.5(4) 108.7(3)
117.8(5) 120.7(4)
113.7(7) 114.2(5)
121.2(8) 123.2(6)
/
/
Cl(2)
80.71(10) 88.48(5)
170.07(11) 88.43(5)
/
/
/
/
Cl(2)
/
/
/
/
108.3(4)
119.2(8)
113.3(11)
118.2(10)
82.40(8)
108.27(16)
122.4(3)
113.6(5)
118.9(5)
88.71(5)
/
P(1)Ã
/C(7)
/
/
/
/N(2)
/
C(13)Ã
/
N(2)
/
C(13)Ã
C(13)Ã
Se(1)
/
N(14)
/
/
N(1)
/
/
C(18)
/
/
P(1)
/
/
Á
Á/
Á/
/
112.45(18)
109.18(18)
114.2(2)
/
/Se(1)
/
/
Se(1)
existence of broad peaks in the 31P{1H} spectrum. Also
in the IR spectrum there appeared to be a shoulder at
1610 cmꢂ1 which also indicated that this complex was
fluxionally chelated.
Reaction of [RuCl2(h3:h3-C10H16)]2 with Ph2PNH-
NHpy gives [RuCl2(h3:h3-C10H16)(Ph2PNHNHpy-P)]
(10) in 42% yield (Table 4). The IR spectrum showed
Fig. 3. The X-ray structure of [RuCl2(h3:h3-C10H16)Ph2PNHNHpy-
P] (10).
ð2Þ
characteristic bands of nNH, nCN[py] and nPN at 3279,
1596 and 984 cmꢂ1, respectively with bands at 305 and
245 cmꢂ1 corresponding to the presence of nRuCl
vibrations. A single resonance was observed in the
31P{1H} NMR spectrum at dp 69.5 ppm. Microanalysis
and FAB mass spectral data gave satisfactory results for
the suggested structure. In the solid state the compound
exhibits monodentate coordination, there is an intramo-
We also prepared [IrCp*Cl2(Ph2PNHNHpy-P] (12).
In the solid state the X-ray structure contains two
independent molecules [the second molecule is num-
bered by addition of 30 to all atom labels]. The bond
lengths and the hydrogen bonding is the same for each
independent molecule. The both display a intramolecu-
˚
lar H
ꢀ ꢀ ꢀ
pairs [N(2)
N(2)ÃH(2N)
/
ꢀ ꢀ ꢀ
/
Cl [N(1)
/
ꢀ ꢀ ꢀ
/
Cl(1) 3.15, H(1N)
/
ꢀ ꢀ ꢀ
ꢀ ꢀ ꢀ
ꢀ ꢀ ꢀ
N(14A) 1798] (Fig. 4).
/
Cl(1) 2.64 A NÃ
/
H/
/
Cl 1128] and intermolecular NH
ꢀ ꢀ ꢀN(14A) 3.09, H(2N)
ꢀ ꢀ ꢀ
/
/N to form dimer
˚
lecular NÃ
/
H
˚
/
ꢀ ꢀ ꢀ
/
Cl H-bond [N(1)
/
ꢀ ꢀ ꢀ
/
Cl(1) 3.75, H(1N)
/
ꢀ ꢀ ꢀ
/
/
/
/
/
N(14A) 2.11 A
Cl(1) 2.99 A NÃ ꢀ ꢀ ꢀCl 1358] (Fig. 3).
/
H
/
/
/
/
/
(3)

1404
A.M.Z. Slawin et al. / Polyhedron 22 (2003) 1397Á1405
/
The reaction of Ph2P(S)NHNHpy with [RuCl2(p-
Cy)]2 [Cyꢀcymene] proceeded in good yield (80%) to
give the chelate complex [Ru(p-Cy)(Ph2P(S)NHNHpy-
/
S,N)][Cl2]. FAB mass spectral analysis gave the ex-
pected fragmentation pattern and parent ion at Mꢂ
/
Cl2ꢀ559. Elemental analysis of this complex gave
/
satisfactory results and the 31P{1H} NMR spectrum
showed a single resonance at dp 81.1 ppm. Analysis by
IR indicated the presence of vibrations at 3448, 3178,
1611, 995 and 635 cmꢂ1 which correspond to nNH, nNH
,
nCN[py], nPN and nPS, respectively. The absence of any
nRuCl vibrations in the IR spectrum indicated that the
complex formed was a chelate and this was further
Fig. 4. The X-ray structure of [IrCp*Cl2(Ph2PNHNHpy P)] (12).
confirmed by the presence of nCN[py] at 1611 cmꢂ1
.
[Cu(MeCN)4][PF6] formed the bis-chelate complex
[Cu(Ph2PNHNHpy)2][PF6] (13) in good yield (71%),
isolated as a cream coloured solid. No NMR data was
observed for this complex since it is paramagnetic.
Microanalysis and FAB mass spectral determination
gave the expected results for the presence of the bis-
chelate complex and this was subsequently confirmed by
the existence of the nCN[py] vibration at 1614 cmꢂ1 in the
IR spectrum.
[Cu(MeCN)4][PF6] reacts with Ph2P(S)NHNHpy si-
milarly to Ph2PNHNHpy to form the bis-chelate com-
plex [Cu(Ph2P(S)NHNHpy-S,N)][PF6], in good yield
(77%). Analysis by 31P{1H} NMR gave a single broad
resonance at dp 65.9 ppm. Elemental analysis confirmed
the suggested bis-chelate structure, as did FAB mass
spectral analysis with the parent ion occurring at Mꢂ
/
PF6ꢀ713. The IR spectrum also confirmed the presence
/
of the bischelate structure with existence of nCN[py]
vibrations at 1611 cmꢂ1. Other vibrations present in
the IR spectrum include nNH, nPN and nPS at 3262, 997
and 622 cmꢂ1, respectively.
4. Supplementary data
(4)
Full lists of structure refinement data, atomic coordi-
nates, bond lengths and angles, anisotropic displace-
ment parameters and hydrogen atom parameters have
been deposited as supplementary material, CCDC Nos.
199 732 and 199 735 at the Cambridge Crystallographic
Data Centre. Copies of this information may be
obtained free of charge from The Director, CCDC, 12
3.2. Coordination chemistry of Ph2P(S)NHNHpy
Similar reactions to those described above can be
performed using Ph2P(S)NHNHpy. Reaction with
[Rh(cod)Cl]2 in toluene formed [Rh(cod)(Ph2P(S)-
NHNHpy-S,N)][Cl] in good yield (79%). Analysis by
Union Road, Cambridge, CB2 1EZ, UK (Fax: ꢁ44-
1223-336-033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk.
/
FAB mass spectrometry gave the parent ion at Mꢂ
/
Clꢂ ꢀ
/536 and microanalysis gave satisfactory results.
The presence of nNH, nCN[py], nPN and nPS vibrations in
the IR spectrum were observed at 3163, 1611, 998 and
640 cmꢂ1, respectively. A single NMR resonance in
CDCl3 was observed in the 31P{1H} spectrum at dp 64.3
ppm. The existence of the nCN[py] vibration at 1611 cmꢂ1
indicated that the complex formed is a chelate with the
Cl acting as a counter ion.
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ð5Þ

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/
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1405
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