Some reactions of azides with diynyl-bis(phosphine)ruthenium-cyclopentadienyl complexes

Article abstract of DOI:10.1016/j.jorganchem.2015.08.019

Reactions of SiMe₃(N₃) with Ru(CCH)(PP)Cp' [PP = (PPh₃)₂, Cp′ = Cp; PP = dppe, Cp′ = Cp?] afford Ru(N₃)(PP)Cp′. Reactions of Ru(CCCCR)(dppe)Cp?with SiMe₃(N₃) give Ru{N₃

Full text of DOI:10.1016/j.jorganchem.2015.08.019

Accepted Manuscript
Some reactions of azides with diynyl-bis(phosphine)ruthenium-cyclopentadienyl
complexes
Michael I. Bruce, Alexandre Burgun, Jonathan George, Brian K. Nicholson, Christian
R. Parker, Brian W. Skelton, Nancy Scoleri, Christopher J. Sumby, Natasha N.
Zaitseva
PII:
S0022-328X(15)30121-2
10.1016/j.jorganchem.2015.08.019
JOM 19207
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 22 July 2015
Revised Date: 21 August 2015
Accepted Date: 21 August 2015
Please cite this article as: M.I. Bruce, A. Burgun, J. George, B.K. Nicholson, C.R. Parker,
B.W. Skelton, N. Scoleri, C.J. Sumby, N.N. Zaitseva, Some reactions of azides with diynyl-
bis(phosphine)ruthenium-cyclopentadienyl complexes, Journal of Organometallic Chemistry (2015), doi:
10.1016/j.jorganchem.2015.08.019.
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ACCEPTED MANUSCRIPT
Some reactions of azides with diynyl-bis(phosphine)ruthenium-cyclopentadienyl complexes
Graphical abstract

ACCEPTED MANUSCRIPT
Correspondence to: Professor M.I. Bruce
School of Chemistry & Physics
University of Adelaide
Adelaide
South Australia 5005
Fax:
E-mail:
+61 8 8313 4358
michael.bruce@adelaide.edu.au
Some reactions of azides with diynyl-bis(phosphine)ruthenium-
cyclopentadienyl complexes
a
a
a
b
Michael I. Bruce, Alexandre Burgun, Jonathan George, Brian K. Nicholson,
a
c
a
a
Christian R. Parker, Brian W. Skelton, Nancy Scoleri, Christopher J. Sumby,
Natasha N. Zaitseva
a
a
Department of Chemistry, School of Physical Sciences, University of Adelaide,
Adelaide, South Australia 5005
Department of Chemistry, University of Waikato, Hamilton, New Zealand
Centre for Microscopy, Characterisation and Analysis, M313, University of
b
c
Western Australia, Crawley, Western Australia 6009
Abstract
Reactions of SiMe (N ) with Ru(C≡CH)(PP)Cp’ [PP = (PPh ) , Cp’ = Cp; PP = dppe,
3
3
3 2
Cp’ = Cp*] afford Ru(N )(PP)Cp’. Reactions of Ru(C≡CC≡CR)(dppe)Cp* with
3
SiMe (N ) give Ru{N C(CN)CH R}(dppe)Cp* (R = H 2, Ph 3). With
3
3
3
2
RuCl(dppe)Cp* in the presence of [NH ]PF , 2 gives binuclear
4
6
[
Cp*(dppe)Ru{N C[{(CN)Ru(dppe)Cp*]CMe}]PF 4. The reaction between TsN
3 6 3
and Ru(C≡CC≡CH)(dppe)Cp* gives Ru{(NC)C=NNTs=CHC(=NTs)}(dppe)Cp* 5,
with a small amount of TsN=PPh CH CH PPh =NTs 6 being obtained from some
2
2
2
2
reactions. X-ray determined structures of Ru(N )(dppe)Cp* and 2-5 are reported,
3
together with plausible routes to 2 and 3.
1

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Introduction
A much used synthetic approach to a variety of molecular building blocks is
the Cu(I)-catalysed [3 + 2]-cycloaddition of azides with alkynes (CuAAC reaction)
[
1,2], a common example of a "click" reaction (Scheme 1) [3]. Several reviews are
available [4-8], including themed issues of at least two journals [9]. This reaction can
also be catalysed by Ag(I) [10] or Ru(II) (the RuAAC reaction) [11,12]. It is of
interest that the latter system affords the 1,5-substituted triazole, while the Cu(I)-
catalysed reaction generally gives the 1,4-isomer (Scheme 1).
R2
N
R1
H
+
N
N
N
N
N
N
R2
N
R2
N
R1
R1
1,4ꢀcycloaddition
1,5ꢀcycloaddition
Scheme 1. 1,4- and 1,5-cycloaddition products from [3 + 2]-cycloaddition of 1-
alkynes to azides.
While applications to organic synthesis are legion, relatively few examples
have involved organometallic substrates. Many electroactive ferrocene-containing
products have been obtained [13], with reactions involving both azidoferrocenes [14]
or alkynylferrocenes [15,16]. Redox-active triazole derivatives of M(CO) Cp were
3
obtained from M(CO) (η-C H N ) and HC≡CAr (Ar = Ph, C H NH -4) [17], while
3
5
4
3
6
4
2
similar additions of azides to Cr(0)-alkynylcarbene complexes [18] and to Ru2
complexes containing alkynylphenyl-amidinate ligands [19], and functionalisation of
Pd L metallo-supramolecular systems [20] have been described.
2
4
Several [3 + 2]-cycloaddition reactions of azido or alkynyl ligands directly
bonded to transition metal centres have been reported recently. These include
addition of a masked alkyne to Mn(N )(CO) (bpy) [21], of C (CO Me) to
3
3
2
2
2
Mo(N )(CO) (en)(η-C H ) [22], and of several alkynes to neutral and cationic Ru(II)
3
2
3
5
azido complexes [23,24].
Unsymmetric Pt(bipy) alkynyls formed by mono-addition of azides to
bis(alkynyl) complexes show enhanced emission and were incorporated into organic
light-emitting diodes (OLEDs) [25]. Reactions of alkynyl-silver(I) compounds with
azides afford metal-free triazoles [26], while many reports describe reactions
involving phosphine-gold(I) alkynyl or azide derivatives such as those applied to the
2

ACCEPTED MANUSCRIPT
synthesis of cytotoxic Au dendrimers [27], the Cu-catalysed click reactions of Au-
alkynyls with PhCH N [28], and the interesting inorganic click reaction between
2
3
Au(N )(PPh ) and Au(C≡CPh)(PPh ) [29]. Similar reactions were later used to
3
3
3
prepare multi-metallic derivatives [30,31].
More relevant to the work to be presented below are reactions of platinum(II)
poly-ynyl complexes with benzyl azide, later extended to the preparation of
permetallated compounds [32].
Results and Discussion
As mentioned above, cycloaddition of activated alkynes HC≡CCO Me and
2
C (CO Me) to Ru(N )(dppe)Cp has been reported to give triazolates
2
2
2
3
Ru{N C R(CO Me)}(dppe)Cp (R = H, CO Me, respectively), in which the
3
2
2
2
heterocyclic ligand is bonded to ruthenium by N(2) [23,24]. To our knowledge, there
are no reports of the reverse reaction, that of organic azides with alkynyl-ruthenium
complexes.
Initial studies showed that reactions of SiMe (N ) with Ru(C≡CH)(PPh ) Cp,
3
3
3 2
Ru(C≡CH)(dppe)Cp* or Ru(C≡CC≡CH)(PPh ) Cp all proceed with metathetic
3
2
replacement of ethynyl or butadiynyl by azide to give known Ru(N )(PP)Cp'
3
complexes [1a; PP = (PPh ) , Cp' = Cp (56%); 1b; PP = dppe, Cp' = Cp* (61%)].
3
2
Consequently, we turned our attention to similar reactions of the diynyl-ruthenium
complexes Ru(C≡CC≡CR)(dppe)Cp* [R = H, Ph, SiMe , Au(PPh )]. The chemistry
3
3
described below is summarised in Schemes 2-4, full details being given in the
Experimental Section.
Addition of SiMe (N ) to solutions of Ru(C≡CC≡CH)(dppe)Cp* in refluxing
3
3
THF resulted in a rapid reaction which afforded the yellow complex 2 in 67% yield,
containing the N C(CN)CMe ligand attached through N(2), as shown by a single
3
crystal X-ray structure determination (see below for details). Azido complex 1b was
also isolated in 8% yield and identified by comparison with an authentic sample and
crystallographically. For Ru{N C(CN)CMe}(dppe)Cp* 2, the IR spectrum contained
3
-1
1
13
bands at 2216 [ν(CN)] and 1724 cm [ν(C=N)]. In the H and C NMR spectra, the
Cp* and dppe ligands gave resonances at δ 1.47, 9.88 and 91.70 (Cp*), 2.29, 3.05 and
1
3
3
(
1.62 (dppe CH ), while the triazole ligand gives rise to C resonances at δ 9.57
2
3
1
Me), 115.42 (CN), 117.71 [C(2)] and 147.10 [C(1)]; the dppe P resonance is at δ
8
8.11 (dppe). The ESI-MS (from a solution containing NaOMe) contained strong
+
+
peaks centred on m/z 765 ([M + Na] ) and 743 ([M + H] ).
The same complex was obtained from Ru(C≡CC≡CSiMe )(dppe)Cp* and
3
SiMe (N ) in similar yield.
3
3
3

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With Ru(C≡CC≡CPh)(dppe)Cp*, a similar reaction with SiMe (N ) afforded
3
3
the related compound Ru{N C(CN)C(CH Ph)}(dppe)Cp* 3 in 13% yield together
3
2
with Ru(N )(dppe)Cp* (43%). Pertinent spectroscopic data for 3 include an IR band
3
-
1
1
at 2213 cm [ν(C≡N)], H NMR signals at δ 1.39 (Cp*), 2.19 and 2.85 (dppe CH ),
2
1
3
3
(
8
.39 (CH Ph), C NMR resonances at δ 10.47 and 92.37 (Cp*), 31.98 (CH Ph), 32.37
2 2
dppe CH ), 118.12 [C(2)], 115.83 (CN), 150.85 [C(1)], and a P NMR signal at δ
8.85 (dppe). In the ESI-MS, peaks at m/z 841 (weak, [M + Na] ) and 818 (strong,
3
1
2
+
+
M ) are present.
A subsequent reaction of Ru{N C(CN)CMe}(dppe)Cp* with an equivalent of
3
RuCl(dppe)Cp* in MeOH, in the presence of [NH ]PF , afforded the yellow binuclear
4
6
complex [Cp*(dppe)Ru{N C[(CN)Ru(dppe)Cp*]CMe}]PF 4 in 68% yield. The IR
3
6
-1
spectra contained bands at 2224 [ν(CN)] and 840 cm [ν(PF)], with duplicated
resonances in the H, C and P NMR spectra arising from the two Ru(dppe)Cp*
centres. The C(2) and C(1) C resonances were at δ 107.50 and 148.12, with the two
dppe groups giving P signals at δ 73.07 and 86.71, along with the PF signal at δ
1
13
31
1
3
3
1
6
1
43.93. In the ESI-MS, the cation was found at m/z 1377. The structure was
confirmed by a single-crystal X-ray study (see below).
[Ru*]
R + TMS
N
N
R = H, TMS, Ph, Au(PPh3)
N
PF6
Ru(dppe)Cp*
N
CN
C
N
N
N
N
(
i)
Cp*(dppe)Ru
N
Cp*(dppe)Ru
N
CH R
Me
2
4
R = H 2; Ph 3
Scheme 2. Synthesis of cyano(alkyl)triazoles from Ru(C≡CC≡CR)(dppe)Cp* (R = H,
SiMe , Ph) and SiMe (N ). Reagent: (i) = RuCl(dppe)Cp* + [NH ]PF .
3
3
3
4
6
The reaction between TsN and Ru(C≡CC≡CH)(dppe)Cp*, carried out in
3
refluxing THF, gave an intractable mixture of products. However, the major product
isolated from a reaction carried out in toluene at r.t. was bright yellow
Ru{(N≡C)C N Ts }(dppe)Cp* 5 (43%) as determined by a single-crystal X-ray
3
2
2
structure determination. Spectroscopic data include ν(CH) at 2977, ν(C≡N) at 2229,
-1
ν(C=N) at 1703 and ν(SO) at 1179 cm . In addition to characteristic signals for the
Ru(dppe)Cp* fragment, the C H protons are at δ 6.61 and 7.68 (both d with J = 8
6
4
Hz) and the Me group a singlet at δ 2.25. The pyrazole ring proton gives a singlet at δ
4

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1
3
1
.23. The C NMR spectrum contains a singlet at δ 21.14 (Me) and pyrazole ring C
at δ 58.52, 116.63, 122.85 (not individually assigned), together with several signals
+
between δ 134.9 and 145.2 from the Ts groups. In the ESI-MS, [M + Na] and [M -
+
H] are at m/z 1073 and 1051, respectively.
Scheme 3. Reaction of Ru(C≡CC≡CH)(dppe)Cp* and TsN to give
3
Ru{(N≡C)C N Ts }(dppe)Cp* 5 and TsN=PPh CH CH PPh =NTs 6.
3
2
2
2
2
2
2
A minor product (3%) was found to be the bis(iminophosphorane)
TsN=PPh CH CH PPh =NTs 6, evidently formed from a Staudinger reaction between
2
2
2
2
displaced dppe and the azide [33,34]. This material was identified from a single-
1
crystal X-ray structure determination (see below). The H NMR spectrum contained
signals at δ 2.33 (Me), 3.12 (dppe) and between δ 7.06 and 7.83 (Ph, C H ). The ESI-
6
4
+
MS from MeOH / NaOMe contained [M + Na] at m/z 759.
Molecular structures
(
a) Ru(N )(dppe)Cp* (1b; Cp = Cp*; PP = dppe). A molecule of this complex is
3
shown in Fig. 1, significant bond parameters being included in Table 1. The usual
coordination within the Ru(dppe)Cp* fragment is found, the almost linear azido
ligand [angle N(1)-N(2)-N(3) 175.8(1)°] being attached via N(1) [Ru-N(1) 2.156(1)
Å; Ru-N(1)-N(2) 122.80(8)°] with the expected bent configuration.
The present structure is similar to that of Ru(N )(PPh ) Cp, which has Ru-P
3
3 2
2
1
.3292(5), 2.3304(5), Ru-N 2.135(3), N-N 1.186(3), 1.164(3) Å, and P-Ru-P
05.22(2), P-Ru-N 85.39(6), 86.65(5), Ru-N-N 124.5(2) and N-N-N 175.2(3)° [35].
5

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Figure 1. A molecule of Ru(N )(dppe)Cp* 1b. Selected bond parameters: Ru-P(1,2)
3
2
2
.2894, 2.2924(3), Ru-C(cp) (av.) 2.225 [range 2.2126-2.2402(12)], Ru-N(1)
.157(1), N(1)-N(2) 1.1917(15), N(2)-N(3) 1.1672(16) Å; P(1)-Ru-P(2) 83.35(1),
P(1,2)-Ru-N(1) 79.80, 87.67(3), Ru-N(1)-N(2) 122.78(8), N(1)-N(2)-N(3)
75.77(13)°. Ellipsoids have been drawn at the 50% probability level with hydrogen
1
atoms and the phenyl carbons of the dppe ligands (except the ipso-carbons) omitted
for clarity.
(
b) Ru{N CRC(CN)}(dppe)Cp* (R = Me 2, CH Ph 3). As shown in Fig. 2 (selected
3
2
bond parameters are in Table 1), in the molecule of 2 the familiar Ru(dppe)Cp* group
is attached to the 1-cyano-2-methyltriazolyl ligand via the central N(1) atom [Ru-N(1)
2
[
1
.107(2) Å]. Within the triazolyl group, atom N(1) is bonded asymmetrically to N(2)
N(1)-N(2) 1.321(2) Å] and N(5) [N(1)-N(5) 1.359(2) Å], with N(2)-N(1)-N(5)
12.4(2)°. Short C-N bonds are consistent with C=N double bonds, while C(3)-C(4)
is also short at 1.384(4) Å, suggesting some degree of delocalisation within the ring.
The CN and Me groups attached to C(3) and C(4), respectively, have no unusual
features. The benzyl complex 3 is similar (selected bond parameters for both
molecules are collected in Table 1). Both variants (2 and 3) are simply close packed
with no significant intermolecular interactions between molecules; in both examples
the nitrile moiety protrudes into a pocket surrounded by aromatic hydrogen atoms but
makes no notable contacts.
6

ACCEPTED MANUSCRIPT
(a)
(b)
Figure 2. (a) A molecule of Ru{N CMeC(CN)}(dppe)Cp* 2. (b) The benzyl
3
derivative 3 is similar. Ellipsoids have been drawn at the 50% probability level with
hydrogen atoms, the phenyl carbons of the dppe ligands (except the ipso-carbons) and
the dichloromethane (2) and benzene (3) solvates omitted for clarity.
(
c) [Cp*(dppe)Ru{N C(CN)[Ru(dppe)Cp*]CMe}]PF 4. Fig. 3 shows a plot of the
3
6
binuclear cation in 4, with selected bond parameters given in Table 1. The complex is
similar to 2, with an Ru(dppe)Cp* group attached to the nitrogen of the CN(31) group
[
Ru(2)-N(31) 2.029(3) Å]. The ligands (dppe and Cp*) of the second Ru(dppe)Cp*
group are twisted by approximately 75° to avert a steric clash between the dppe
ligands of Ru(1) and Ru(2). Bond parameters are overall similar to those found in 2
and in [Ru(NCMe)(PPh ) Cp*]PF [Ru-NC 2.056(2) Å ] [36]. Molecules of 4 pack in
3
2
6
the triclinic space group P1 with small solvate-filled channels (ethanol) percolating
down the a-axis of the crystal. As with the mononuclear complexes above no obvious
intermolecular interactions dominate the packing.
7

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Figure 3. A plot of a molecule of [Cp*(dppe)Ru{N C[CN{Ru(dppe)Cp*}]CMe}]PF
3
6
4
. Ellipsoids have been drawn at the 50% probability level with hydrogen atoms, the
phenyl carbons of the dppe ligands (except the ipso-carbons) and the
hexafluorophosphate anion, which is disordered over three positions, omitted for
clarity.
(d) Ru[(NC)C=NNTs=CC=NTs}(dppe)Cp* 5. A molecule of 5 is shown in Figure 4,
from which it can be seen that a N=C N iminopyrazole ring, bearing tosyl groups on
3
2
N(4) and N(6), is attached via N(1) of the N(1)≡C(2) group [N(1)-C(2) 1.148(5) Å] to
the familiar Ru(dppe)Cp* fragment [Ru-N(1) 2.006(3) Å]. The C N ring is similar to
3
2
that found in 3,5-diaminopyrazolone-4-oxime [37].
8

ACCEPTED MANUSCRIPT
Figure 4. A molecule of Ru{(NC)C=NNTs=CC=NTs}(dppe)Cp* 5. Ellipsoids have
been drawn at the 50% probability level with hydrogen atoms, the phenyl carbons of
the dppe ligands (except the ipso-carbons) and the disorder of the tolyl ring of the
tosyl group attached at N(6) omitted for clarity.
(
e) TsN=PPh CH CH PPh =NTs 6. This centrosymmetric molecule is depicted in
2 2 2 2
Fig. 5, with selected bond parameters given in the caption thereto. The geometry is
similar to that found for TsN=PPh [cf. N-P 1.579(4), N-S 1.586(4) Å; S-N-P
3
1
26.4(2)° [38]] and deserves no further comment.
Figure 5. A molecule of TsN=PPh CH CH PPh =NTs 6. Selected bond parameters:
2
2
2
2
C(10)-P(1) 1.817(11), P(1)-N(1) 1.575(9), N(1)-S(1) 1.582(10), S(1)-O(2,3) 1.448(3),
9

ACCEPTED MANUSCRIPT
1
1
.447(3), C(10)-C(10') 1.510(10) Å; P(1)-C(10)-C(10') 113.1(6), C(10)-P(1)-N(1)
15.1(6), P(1)-N(1)-S(1) 134.7(6), N(1)-S(1)-O(2,3) 104.4(4), 110.8(5), N(1)-S(1)-
C(31) 112.2(3), O(2)-S(1)-O(3) 116.2(2)°. Ellipsoids have been drawn at the 50%
probability level with hydrogen atoms, the phenyl carbons of the dppe ligands (except
the ipso-carbons) and the disorder of the N=PPh omitted for clarity.
Discussion
The reactions described above are notable for not producing the expected
triazolyl complexes, at least under the conditions employed here (which differ from
those commonly employing Cu(I) or Ru(II) catalysts). Further reaction with the free
C≡C triple bond has occurred to give the cyano-methyl (or -benzyl) -triazolyl ligands
found by the single-crystal X-ray structure determinations.
Of some interest is the course of the reactions described above. A possible
mechanism for the formation of 2 and 3 is shown in Scheme 4. Nucleophilic addition
of TMS azide to C(1) of the diynyl ligand and addition of a proton (from solvent) is
followed by cycloaddition of a second TMS azide to C2 and C3. Rearrangement by
tandem protodesilylation is then followed by loss of N and of a proton to give the CN
2
group. Migration of the [Ru*] fragment to the central N of the triazole affords the
isolated product.
1
0

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TMS
Ru*]
N
N
N
N
N
TMS
N
R
H
[
R
H
[
Ru*]
N
N
N
TMS
N
N
N
TMS
N
N
H
N
R
R
[Ru*]
[Ru*]
N
N
N
N
TMS
TMS
N
H
N
H
N
N
N
N
R
R
[Ru*]
N
N
N
N
N
N
[Ru*]
H
R = H 2 ; Ph 3
Scheme 4. Formation of 2 or 3 by addition of two molecules of SiMe (N ) to
3
3
precursor diynyl complexes Ru(C≡CC≡CR)(dppe)Cp* (R = H or Ph, respectively).
Derivatisation of 3 was carried out by reaction with RuCl(dppe)Cp* in THF,
which afforded binuclear [Cp*(dppe)Ru{N C[CNRu(dppe)Cp*]CMe}]PF 4.
3
6
Coordination of the second Ru(dppe)Cp* moiety to N(31) of the ligand in 3 has
occurred.
Reactions of sulfonyl azides with alkynes have been found to give products
which depend upon conditions and reagents and may include N-sulfonylamidines
when amines are present, or N-sulfonylamides in the presence of water [40].
From a reaction of Ru(C≡CC≡CH)(dppe)Cp* with TsN , triazolyl complex 5
3
was obtained. The structural study suggests that reaction with the outer C≡C triple
bond has occurred, the resulting iminopyrazolyl ligand bearing a -C≡N-Ru(dppe)Cp*
substituent on C(1). In the course of this reaction, one molecules of N is formally
2
1
1

ACCEPTED MANUSCRIPT
eliminated, although the precise mechanism of this reaction is unclear. The Staudinger
bis(iminophosphorane) TsN=PPh CH CH PPh =NTs 6 was obtained, although only
2
2
2
2
in minor amount, from this reaction. Combination of dppe (presumably displaced
from Ru during the reaction) with nitrene TsN would afford this compound.
Conclusions
Reactions of SiMe (N ) with complexes such as Ru(C≡CH)(PP)Cp’ [PP =
3
3
(
PPh ) , Cp’ = Cp; PP = dppe, Cp’ = Cp*] result in metathetical displacement of the
3 2
ethynyl group by azide, rather than the [3 + 2]-cycloaddition to give triazoles
expected from “click” reactions. The diynyl Ru(C≡CC≡CH)(PPh ) Cp reacts
3
2
similarly. However, formation of a substituted triazole occurs when SiMe (N ) reacts
3
3
with Ru(C≡CC≡CH)(dppe)Cp*, in which the diynyl group is more strongly attached
to the metal centre, while not possessing the tendency for the PR ligand to dissociate
3
as is often found with the (PPh ) analogues. Nevertheless, formation of 6 shows that
3
2
decoordination of dppe is possible and may occur to a degree.
Formation of the triazole is accompanied by further reaction to give the CN
and alkyl substituents (Scheme 2). A related reaction using tosyl azide afforded a
cyano-substituted pyrazole, in a reaction involving two molecules of azide (Scheme
4
).
It is evident that this chemistry is somewhat removed from the “click”
chemistry found by others in the reactions of various azides with alkynyl metal
complexes. The relatively low yields of the metal complexes also argues against
conventional “click” mechanisms being operative here. While detailed discussion of
possible mechanisms is inappropriate at this stage, defining factors may involve the
steric hindrance attendant on the approach of reagents to the diynyl group, resulting
from the presence of relatively bulky dppe and Cp* ligands on the metal centre.
None of the reactions described above were carried out in the presence of the
usual Cu or Ru catalysts used in conventional “click” chemistry. Further work is
necessary to determine the effect of the metal centre upon the reactivity of the diynyl
group towards azide.
1
2

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Experimental
General. All reactions were carried out under dry nitrogen, although normally no
special precautions to exclude air were taken during subsequent work-up. Common
solvents were dried, distilled under nitrogen and degassed before use. Separations
were carried out by preparative thin-layer chromatography on glass plates (20 x 20
2
cm ) coated with silica gel (Merck, 0.5 mm thick).
Instruments. IR spectra were obtained on a Bruker IFS28 FT-IR spectrometer.
Spectra in CH Cl were obtained using a 0.5 mm path-length solution cell with NaCl
2
2
windows. Nujol mull spectra were obtained from samples mounted between NaCl
1
discs. NMR spectra were recorded on a Varian Gemini 2000 instrument ( H at
13
31
3
00.145 MHz, C at 75.479 MHz, P at 121.501 MHz). Unless otherwise stated,
samples were dissolved in CDCl contained in 5 mm sample tubes. Chemical shifts
3
1
13
are given in ppm relative to internal tetramethylsilane for H and C NMR spectra
and external H PO for P NMR spectra. Electrospray mass spectra (ES-MS) were
31
3
4
obtained from samples dissolved in MeOH, with added NaOMe to aid ionisation [41].
Solutions were injected into a Fisons VG Platform II spectrometer via a 10 ml
injection loop. Nitrogen was used as the drying and nebulising gas. Elemental
analyses were by Campbell Microanalytical Laboratory, University of Otago,
Dunedin, New Zealand.
Reagents. Ru(C≡CC≡CR)(dppe)Cp* [R = H [42], Ph [43] , SiMe [42], Au(PPh )
3
3
[
42]], Ru(C≡CH)(PPh ) Cp [44], Au(N )(PPh ) [45] were made by the cited methods.
3 2 3 3
SiMe (N ), (tos)N were commercial samples (Sigma-Aldrich).
3
3
3
Reactions of SiMe (N )
3
3
(
a) With Ru(C≡CC≡CH)(dppe)Cp*. SiMe (N ) (14 mg, 0.12 mmol) was added to a
3 3
solution of Ru(C≡CC≡CH)(dppe)Cp* (40 mg, 0.06 mmol) in THF (5 ml) and the
mixture was heated at reflux point for 2 h. Removal of THF, dissolution of the
residue in CH Cl and separation by preparative TLC (silica gel, acetone / hexane =
2
2
3
/7) gave two bands. The bright yellow fraction (R = 0.75) gave
f
Ru{N C(CN)CMe}(dppe)Cp* 2 (29.1 mg, 67%) as yellow crystals (from benzene /
3
hexane). Anal. Found: C, 65.77; H, 6.25; N, 7.00. Calcd (C H N P Ru.0.5C H ):
4
0
42
4
2
6
6
-1
C, 65.80; H, 6.29; N, 7.14; M, 742. IR (CH Cl , cm ): ν(C≡N) 2216m, ν(C=N)
724m. H NMR (C D ): δ 1.47 (s, 15H, Cp*), 1.67 (s, 3H, Me), 2.29, 3.05 (2 x m,
6 6
H, dppe), 6.99-7.25 (m, 20H, Ph). C NMR (C D ): δ 9.57 (s, Me), 9.88 (s,
2
2
1
1
4
1
3
6
6
C Me ), 31.62 (m, dppe), 91.70 (s, C Me ), 115.42 (s, CN), 117.71 (s, C ), 127.67-
5
5
5
5
2
3
1
1
41.78 (m, Ph); 147.10 (s, C1). P NMR (C D ): δ 88.1 (s, dppe). ES-MS, MeOH-
6 6
NaOMe, m/z): 765.187, [M + Na] (calcd 765.183); 743.204, [M + H] (calcd
43.201); 635, [Ru(dppe)Cp*] .
+
+
+
7
The second dark yellow band (R = 0.52) yielded Ru(N )(dppe)Cp* (3.3 mg, 8%),
f
3
identified by comparison with an authentic sample.
1
3

ACCEPTED MANUSCRIPT
Similarly, 2 (21 mg, 38%) was obtained from Ru(C≡CC≡CSiMe )(dppe)Cp* (51 mg,
3
0
.07 mmol) and SiMe (N ) (9 µL, 0.07 mmol), and also from
3 3
Ru{C≡CC≡CAu(PPh )}(dppe)Cp* or Ru(C≡CC≡CSiMe )(dppe)Cp* and SiMe (N ).
3
3
3
3
(
b) With Ru(C≡CC≡CPh)(dppe)Cp*. SiMe (N ) (9.1 mg, 0.08 mmol) was added to
3 3
a solution of Ru(C≡CC≡CPh)(dppe)Cp* (30 mg, 0.04 mmol) in THF (7 ml). After
heating at reflux for 6 h, THF was removed, the residue dissolved in acetone and
separated by preparative TLC (SiO , acetone / hexane = 1/3). The yellow band (R =
2
f
0
.58) gave Ru{N C(CN)C(CH Ph)}(dppe)Cp* 3 (4.1 mg, 13%) as yellow crystals
3 2
(
from benzene / hexane). Anal. Found: C, 68.81; H, 5.81; N, 6.45. Calcd
-1
(C H N P .0.5C H ): C, 68.59; H, 5.76; N, 6.53; M, 818. IR (CH Cl , cm ):
4
6
46
4
2
6
6
2
2
-1
1
ν(CN) 2213 cm . H NMR (C D ): δ 1.39 (s, 15H, Cp*), 2.19, 2.85 (2 x m, 4H,
dppe), 3.39 (s, 2H, CH ), 6.65-7.18 (m, 25H, Ph). C NMR (C D ): δ 10.47 (s,
6
6
1
3
2
6
6
C Me ), 31.98 (s, CH ), 32.37 (m, dppe), 92.37 (s, C Me ), 115.83 (s, CN), 118.12 (s,
5
5
2
5
5
3
1
C ), 126.36-142.65 (m, Ph), 150.85 (s, C ). P NMR (C D ): δ 88.9 (s, dppe). ES-
2
1
6
6
+
+
MS (MeOH-NaOMe, m/z): 841.228, w, [M + Na] (calcd 841.215); 818.238, s, [M]
calcd 818.225).
(
The second dark yellow band (R = 0.47) contained Ru(N )(dppe)Cp* (11.6 mg,
f
3
4
3%), identified by comparison with an authentic sample.
(
c) With Ru(C≡CC≡CH)(PPh ) Cp. SiMe (N ) (0.92 mg, 0.08 mmol) was added to
3
2
3
3
a solution of Ru(C≡CC≡CH)(PPh ) Cp (30 mg, 0.04 mmol) in THF (8 ml) and the
3
2
mixture was stirred at 65°C (oil bath) for 6 h. Removal of THF, extraction with
acetone and purification by preparative TLC (SiO , acetone / hexane = 3/7) gave one
2
yellow band (R = 0.41) containing Ru(N )(PPh ) Cp (16.7 mg, 56%) as yellow-
f
3
3 2
orange crystals (from benzene / hexane), identified by comparison with an authentic
-
1
1
sample. IR (CH Cl , cm ): ν(N ) 1981 (m). H NMR (CDCl ): δ 7.70-6.79 (m, 30H,
3 3
2
2
1
3
Ph); 4.26 (s, 5H, Cp). C NMR (CDCl ): δ 134.04-125.97 (m, Ph); 86.03 (s, C H ).
3
5
5
3
1
+
P NMR (CDCl ): δ 43.3 (s, PPh ). ES-MS (MeOH, m/z): 733, [M] ; 691,
Ru(PPh ) Cp] ; 429, [Ru(PPh )Cp] .
3 2 3
3
3
+
+
[
(
d) With Ru(C≡CH)(PPh ) Cp. A mixture of Ru(C≡CH)(PPh ) Cp (37 mg, 0.05
3 2 3 2
mmol) and SiMe N (12 mg, 0.1 mmol) in THF (5 ml) was stirred at r.t. for 48 h.
3
3
Removal of THF, extraction with benzene and purification on a short column of SiO2
eluant acetone / hexane = 1/3) gave a single yellow band containing
Ru(N )(PPh ) Cp (13.7 mg, 36.2 %) as a yellow-orange powder.
(
3
3 2
(e) With Ru(C≡CH)(dppe)Cp*. As in (d), a mixture of Ru(C≡CH)(dppe)Cp* (25 mg,
0
.04 mmol) and SiMe N (9.2 mg, 0.08 mmol) in THF (6 ml) after 72 h at r.t. gave
3
3
-1
1
orange Ru(N )(dppe)Cp* (15.6 mg, 61%). IR (CH Cl , cm ): ν(N ) 2035 (s). H
3
2
2
3
NMR (C D ): δ 7.25-7.07 (m, 20H, Ph); 2.37-2.35, 1.98-1.85 (2 x m, 2 x 2H,
6
6
1
4

ACCEPTED MANUSCRIPT
3
1
CH CH ); 1.53 (s, 30H, Cp*). P NMR (C D ): δ 77.7 (s, dppe). ES-MS (+ve ion,
2
2
6
6
+
+
MeOH, m/z): 700, [M+ Na] ; 635, [Ru(dppe)Cp*] .
Reaction of 2 with RuCl(dppe)Cp*.
A mixture of 2 (25.5 mg, 0.034 mmol) and RuCl(dppe)Cp* (23 mg, 0.034 mmol) and
NH PF (22.6 mg, 0.136 mmol) in MeOH (15 ml) was heated at reflux point for 4 h.
4
6
Evaporation of the yellow solution, extraction of the residue with benzene and
purification by TLC (SiO , acetone / hexane = 1/2) gave a yellow band (R = 0.42)
2
f
containing [Cp*(dppe)Ru{N C[CNRu(dppe)Cp*]CMe}]PF 4 (35.5 mg, 67.5%),
3
6
which formed yellow crystals from EtOH. Anal. Found: C, 59.63; H, 5.57; N, 3.62.
Calcd (C H F N P Ru ): C, 59.91; H, 5.36; N, 3.68; M (cation), 1377. IR
7
6
81
6
4
5
2
-1
1
(
CH Cl , cm ): ν(CN) 2224, ν(PF) 840. H NMR (CDCl ): δ 1.36 (s, 15H, Cp*),
2
2
3
1
2
.40 (s, 15H, Cp*), 1.64 [s(br), 3h, Me], 2.17 [m, 4H, dppe of CN-Ru(dppe)Cp*],
.47, 2.88 [2 x m, 4H, N-Ru(dppe)Cp*], 7.08-7.47 (m, 40H, Ph). C NMR (CDCl3):
1
3
δ 9.09 (s, Me), 9.25 (s, C Me ), 9.36 (s, C Me ), 28.10 (m, dppe), 31.16 (m, dppe),
5
5
5
5
9
1.70 (s, C Me ), 92.24 (s, C Me ), 107.50 (s, C ), 124.22-140.26 (m, Ph), 148.12 (s,
5 5 5 5 2
31
C1). P NMR (CDCl ): δ 73.07 [s(br), 2P, CN-Ru(dppe)Cp*], 86.71 [s(br), 2P, N-
3
Ru(dppe)Cp*], -143.93 [sept, J(PF) 710 Hz, 1P, PF ]. ES-MS (MeOH, m/z):
6
+
1
377.341, [M] (calcd 1377.353).
Reaction of Ru(C≡CC≡CH)(dppe)Cp* with TsN3.
a) In toluene. A solution of Ru(C≡CC≡CH)(dppe)Cp* (31 mg, 0.05 mmol) in
(
toluene (10 mL) was treated with TsN (28 mg, 0.14 mmol) and stirred at r.t. for 18 h.
3
The solvent was then evaporated to ca 2 mL and hexane (30 mL) was added dropwise.
A yellow precipitate formed and was filtered on sintered funnel and washed with
hexane to give Ru{CN[C N H(NTs)(Ts)]}(dppe)Cp* 5 as a bright yellow crystalline
3
2
powder (33 mg, 43%). Single crystals suitable for X-ray studies were grown from
-
1
THF/hexane. IR (CH Cl , cm ):
ν
(C-H) 2977 (m);
ν
(C≡N) 2229 (m);
ν
(C=N) 1703
2
2
1
2
(m);
ν
(SO) 1179 (m). H NMR (C D ): δ 7.68 (d, J(HH) 8 Hz, 2H, C H ); 7.23-6.95
6
6
6
4
2
(
m, 20H, Ph); 6.61 (d, J(HH) 8 Hz, 2H, C H ); 2.25 (s, 3H, CH ); 2.04-1.99, 1.89-
.85 (2 x m, 2 x 2H, CH CH ); 1.49 (s, 15H, Cp*); 1.23 (s, 1H, CH). C NMR
2 2
6 4 3
1
3
1
(
C D ): δ 145.17, 144.89, 138.84, 134.87 (4 x s, C H ); 130.39-127.06 (m, Ph);
6 6 6 4
1
16.63 (s, C); 122.85 (s, C); 92.27 (s, C Me ); 58.52 (s, C); 28.77-28.18 (m,
5 5
31
CH CH ); 21.14 (s, CH ); 9.79 (s, C Me ). P NMR (C D ): δ 74.3 (s, dppe). ES-MS
2
2
3
5
5
6
6
+
+
+
(+ve ion, MeOH, m/z): 1073, [M + Na] ; 1051, [M + H] ; 635, [Ru(dppe)Cp*] . High
+
resolution MS (m/z): 1051.224, [M + H] .
(
b) In THF. A solution of TsN (28.8 mg, 0.146 mmol) in THF (1 ml) was added to
3
one of Ru(C≡CC≡CH)(dppe)Cp* (50 mg, 0.073 mmol) in THF (5 ml), and the
mixture was heated at reflux point for 4 h. Removal of THF, and purification of a
CH Cl extract of the residue (SiO , acetone / hexane = 2/3) gave several minor
2
2
2
products together with a pale yellow band (R = 0.58), from which
f
TsN=PPh CH CH PPh =NTs 6 (1.8 mg, 3 %) was isolated as colourless crystals
2
2
2
2
1
5

ACCEPTED MANUSCRIPT
1
(
7
from benzene). H NMR (CDCl ): δ 2.33 (s, 6H, 2Me), 3.12 (m, 4H, dppe), 7.06-
3
3
1
.83 (m, 28H, 4Ph + 2 C H ). P NMR (CDCl ): δ 19.68 (s, dppe). ES-MS (MeOH-
6 4 3
NaOMe, m/z): 759.177, [M + Na] (calcd 759.164).
+
Structure Determinations
Data for the structures were collected at 100K (110K for 3 and 4) on either an Oxford
Diffraction Gemini (for compounds 1b, 2, 5 and 6) or an Xcalibur (for 3 and 4)
diffractometer with Mo Kα radiation, λ = 0.71073 Å (Cu Kα, λ = 1.54178 Å for 5).
Data were corrected for absorption [47] and the structures solved by direct methods
2
and refined by full-matrix least squares on F using SHELXL-2014 [46] interfaced
through the program X-Seed [48] or WinGX [49]. Unless stated below, anisotropic
displacement parameter forms were refined for the non-hydrogen atoms, hydrogen
atom treatment following riding models.
Pertinent results are given in the Figures (which in general show non-hydrogen atoms
with 50% probability amplitude displacement ellipsoids/ and in captions to the
Figures and Table 1; crystal data and refinement details are collected in Tables 2 and
3
.
Special refinement details
. The solvent was modelled as a dichloromethane molecule disordered over two sets
2
of sites with occupancies constrained to 0.5 after trial refinement. Geometries were
restrained to ideal values.
3
. The crystal was small and relatively weakly diffracting, thus data above 2θ = 50°
were omitted from the refinement.
. The PF anion was modelled with occupancy over three sites (0.4, 0.4, 0.2
4
6
occupancy) and the minor occupancy site was refined with isotropic displacement
parameters. Two EtOH molecules were modelled (both at 50% occupancy, isotropic
displacement parameters) and one of these shares the low occupancy PF site.
6
5
. One tosyl group was modelled as being disordered over two sets of sites with
occupancies constrained to 0.5 after trial refinement. The solvent was modelled as a
dichloromethane molecule with site occupancies refined to 0.293(4). Partially
weighted atoms were refined with isotropic displacement parameters.
6
. One phenyl ring, 11n, together with the associated P an N atoms were modelled as
being disordered over two sets of sites with site occupancies constrained to 0.5 after
trial refinement.
Supplementary Material
CIFs for the X-ray structure determinations of Ru(N )(dppe)Cp* 1b,
3
Ru{N CRC(CN)}(dppe)Cp* (R = Me 2, CH Ph 3),
3
2
[
Ru{N CMeC(CN)[Ru(dppe)Cp*]}(dppe)Cp* 4,
3
Ru{N≡CC=NNTs=CC(=NTs)}(dppe)Cp* 5, (TsN=PPh CH ) 6. CCDC 1409117-
2
2 2
1
409122, respectively, contain the supplementary crystallographic data for this paper.
1
6

ACCEPTED MANUSCRIPT
These data can be obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.ca.ac.uk/data_request/cif.
1
7

ACCEPTED MANUSCRIPT
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[
[
48] L.J. Barbour, J. Supramol. Chem. 1 (2001) 189.
49] L.J. Farrugia, J. Appl. Cryst. 45 (2012) 849.
2
0

ACCEPTED MANUSCRIPT
Table 1. Selected bond distances (Å) and angles (deg.)
Parameter
2
2.2908(6)
2.2922(6)
3
2.3029(10)
2.2885(10)
4
2.2988(10)
2.2961(10)
2.2965(10)
2.2985(10)
2.110(3)
5
2.3011(12)
2.3066(12)
Ru(1)-P(1)
Ru(1)-P(2)
Ru(2)-P(3)
Ru(2)-P(4)
Ru(1)-N(1)
Ru(2)-N(31)
Ru(1)-C(cp) (av.)
2.107(2)
2.2362
2.107(3)
2.242
2.006(3)
2.029(3)
2.236
2.219
[
2.220-2.246(3)] [2.225-2.266(3)]
[2.223-2.249(4)]
2.231
[2.210-2.228(4)]
Ru(2)-C(cp) (av.)
N(1)-N(2)
[
2.205-2.250(4)]
1.321(2)
1.325(4)
1.324(4)
1.338(5)
[
N(6)-N(7)]
N(1)-N(5)
C(3)-N(2)
1.359(2)
1.361(2)
1.351(4)
1.363(4)
1.348(4)
1.360(5)
1.334(6)
C(3)-N(7)]
[
C(4)-N(4)
C(4)-N(5)
1.373(6)
1.380(7)
1.337(3)
1.340(4)
1.338(5)
[
C(5)-N(6)]
C(3)-C(4)
1.384(3)
1.419(3)
1.145(3)
1.498(3)
1.389(5)
1.420(5)
1.154(4)
1.498(4)
1.394(5)
1.420(5)
1.146(5)
1.493(6)
1.436(7)
C(3)-C(31)
C(31)-N(31)
C(4)-C(41)
1.368(6)
[
C(4)-C(5)]
C(41)-C(42)
1.520(5)
83.55(3)
84.42(8)
P(1)-Ru(1)-P(2)
P(1)-Ru(1)-N(1)
83.41(2)
86.04(5)
83.56(3)
87.22(8)
85.19(11)
21

ACCEPTED MANUSCRIPT
P(2)-Ru(1)-N(1)
P(3)-Ru(2)-P(4)
P(3)-Ru(2)-N(31)
Ru(1)-N(1)-N(2)
Ru(1)-N(1)-N(5)
Ru(2)-N(31)-C(31)
87.31(6)
89.40(8)
85.32(9)
83.35(4)
90.83(9)
122.8(2)
124.5(2)
172.2(3)
85.15(11)
173.4(4)
124.85(17)
122.77(18)
122.6(2)
124.0(2)
[
Ru(1)-N(1)-C(2)]
C(3)-N(2)-N(1)
N(2)-N(1)-N(5)
C(4)-N(5)-N(1)
N(5)-C(4)-C(3)
N(2)-C(3)-C(4)
C(3)-C(4)-C(41)
C(4)-C(3)-C(31)
C(3)-C(31)-N(31)
C(4)-C(41)-C(42)
105.0(2)
112.4(2)
106.2(2)
107.3(2)
109.1(2)
130.4(3)
128.9(3)
177.3(3)
104.8(3)
112.9(3)
106.0(3)
107.4(3)
108.8(3)
127.5(3)
130.4(3)
178.2(4)
119.3(3)
105.0(3)
112.7(3)
106.3(3)
107.2(3)
108.7(3)
129.9(4)
129.74)
177.4(4)
For 5: C(2)-C(3) 1.435(6) Å; N(1)-C(2)-C(3) 179.0(5), C(4)-C(3)-N(7) 113.7(4), C(3)-C(4)-C(5) 103.1(5),
C(3)-C(4)-N(4) 122.3(4), C(4)-C(5)-N(6) 106.3(5), C(5)-N(6)-N(7) 114.4(6), C(3)-N(7)-N(6) 102.4(4)°.
22

ACCEPTED MANUSCRIPT
Table 2. Crystal data and structure refinement for 1, 2, 3 and 4.
Compound
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
1b
2
3
4
C H N P Ru
C H Cl N P Ru
C H N P Ru
C H F N OP Ru
2
36
39
3
2
41 44
2
4
2
49 49
4
2
78 87
6
4
5
676.71
100(2)
0.71073
triclinic
826.71
100(2)
0.71073
856.93
110(2)
0.71073
1567.50
110(2)
0.71073
triclinic
monoclinic
monoclinic
P2 /n
P2 /c
1
1
P1
P1
a (Å)
b (Å)
c (Å)
α (º)
β (º)
γ (º)
10.0844(3)
11.8343(2)
13.1251(4)
88.151(2)
82.945(2)
89.216(2)
1553.63(7)
2
16.9146(6)
11.8508(4)
21.1555(5)
13.0769(3)
13.1142(4)
24.1054(8)
12.7430(3)
15.8051(5)
20.3273(7)
89.272(3)
72.631(3)
86.020(2)
3897.8(2)
2
102.648(3)
100.105(3)
3
Volume (Å )
4137.7(2)
4
4069.8(2)
4
Z
3
Density (calc.) (Mg/m )
Absorption coefficient (mm )
1.447
0.638
1.327
0.618
1.399
0.504
1.336
0.549
-1
3
Crystal size (mm )
0.29 x 0.18 x 0.075 0.36 x 0.18 x 0.04 0.16 x 0.03 x 0.03 0.46 x 0.40 x 0.20
θ range for data collection (º)
Reflections collected
2.923 to 37.394
37660
2.617 to 31.773
50423
2.475 to 28.181
28470
2.514 to 29.240
35337
Independent reflections [R(int)]
Completeness (%) [θmax (°)]
Data / restraints / parameters
15475 [0.0254]
99.3 [36.5]
13238 [0.0670]
99.9 [30]
8518 [0.0807]
98.4 [26]
8518 / 0 / 510
1.033
17527 [0.0327]
96.1 [27]
15475 / 0 / 384
0.972
13238 / 4 / 484
0.890
17527 / 8 / 967
1.107
2
Goodness-of-fit on F
R1 [I>2σ(
Ι)]
0.0293
0.0425
0.0512
0.0509
wR (all data)
0.0751
0.1029
0.0913
0.1652
2
-3) 1.431 and -0.466
Largest diff. peak and hole (e.Å
1.211 and -0.807 0.525 and -0.650
1.523 and -0.623
23

ACCEPTED MANUSCRIPT
Table 3. Crystal data and structure refinement for 5 and 6.
Compound
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
a (Å)
5
6
C54.29H54.59Cl0.59N O P RuS
C H N O P S
40 38 2 4 2 2
4
4
2
2
1075.13
100(2)
1.54178
736.78
100(2)
0.71073
monoclinic
monoclinic
P2 /n
P2 /n
1
1
12.1705(3)
14.5774(3)
28.2919(6)
98.030(2)
4970.17(19)
4
10.5275(9)
9.4570(11)
17.9939(18)
98.174(9)
1773.2(3)
2
b (Å)
c (Å)
β (º)
Volume (Å )
3
Z
3
Density (calc.) (Mg/m )
1.437
4.644
0.17 x 0.07 x 0.015
3.155 to 67.288
37626
1.380
0.286
0.39 x 0.25 x 0.09
2.909 to 25.999
12563
-1
Absorption coefficient (mm )
3
Crystal size (mm )
θ range for data collection (º)
Reflections collected
Independent reflections [R(int)]
Completeness (%) [θmax (°)]
Data / restraints / parameters
8679 [0.0747]
98.2 [66.5]
8679 / 21 / 627
0.849
3484 [0.0558]
99.9 [25.24]
3484 / 145 / 308
1.155
2
Goodness-of-fit on F
R1 [I>2σ(
Ι)]
0.0420
0.0769
wR (all data)
0.0967
0.1598
2
-3)
0.962 and -0.675
0.333 and -0.434
Largest diff. peak and hole (e.Å
24

ACCEPTED MANUSCRIPT
Some reactions of azides with diynyl-bis(phosphine)ruthenium-cyclopentadienyl complexes
(
M.I. Bruce et al.)
Highlights
•
Alkyl azides (two equiv.) and diynyl-ruthenium complexes give alkyl-cyano-triazolyl
complexes
•
•
Tosyl azide and diynyl complex affords a tosylimino-cyano-pyrazolyl-ruthenium complex
X-ray crystal structures of four ruthenium complexes have been determined