Gold(I) complexes of neutral, anionic, and oxidized bis(diphenylphosphino) acetonitrile

Article abstract of DOI:10.1016/j.inoche.2011.10.030

The ligand bis(diphenylphosphino)acetonitrile, (PPh₂) ₂CHCN, ("dppm-CN"), was prepared. The reaction between dppm-CN and [Au(C₆F₅)(tht)] (tht = tetrahydrothiophene) (molar ratio 1:2) formed an open-ended dinuclear gold(I) complex [(AuC ₆F₅)₂(dppm-CN)], 1. The crystal structure showed a linear disposition of dimers with intramolecular Au???Au interactions between the dinuclear units, but despite two distinctly different distances between the gold centers, it is without intermolecular Au???Au interactions. Deprotonation of dppm-CN afforded the anion [(PPh₂)₂CCN] which reacted with [AuCl(tht)] (molar ratio 1:1) to form a neutral cyclic dinuclear gold(I) complex [Au ₂{(PPh₂)₂CCN}₂], 2. Complex 2 could also be formed from mono- or bis(phosphine) gold(I) chloride complexes through the making and breaking of Au-P bonds. Reaction between the oxidized, deprotonated form of the ligand, [(P(S)Ph₂)₂CCN], and [AuCl(PPh₃)] (molar ratio 1:1) formed the neutral mononuclear complex [Au(PPh₃)(P(S)Ph₂)₂CCN] 3, with the [AuPPh₃]⁺ fragment bonded to one sulfur atom and a large degree of electron delocalization across the S-P-C-P-S ring. Complexes 1-3 were all obtained in satisfactory yield (70-90%), and analyzed by single crystal X-ray studies, solution ¹H and ³¹P NMR, IR, and elemental analyses.

Full text of DOI:10.1016/j.inoche.2011.10.030

Inorganic Chemistry Communications 15 (2012) 216–220
Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Gold(I) complexes of neutral, anionic, and oxidized bis
(diphenylphosphino)acetonitrile
Sicelo V. Sithole a, Richard J. Staples b, Werner E. van Zyl a,
⁎
a
School of Chemistry, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban 4000, South Africa
b
Department of Chemistry, Michigan State University, East Lansing, MI 48824–1322, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
The ligand bis(diphenylphosphino)acetonitrile, (PPh2)2CHCN, (“dppm-CN”), was prepared. The reaction be-
tween dppm-CN and [Au(C6F5)(tht)] (tht=tetrahydrothiophene) (molar ratio 1:2) formed an open-ended
dinuclear gold(I) complex [(AuC6F5)2(dppm-CN)], 1. The crystal structure showed a linear disposition of di-
mers with intramolecular Au···Au interactions between the dinuclear units, but despite two distinctly differ-
ent distances between the gold centers, it is without intermolecular Au···Au interactions. Deprotonation of
dppm-CN afforded the anion [(PPh2)2CCN]¯ which reacted with [AuCl(tht)] (molar ratio 1:1) to form a neu-
tral cyclic dinuclear gold(I) complex [Au2{(PPh2)2CCN}2], 2. Complex 2 could also be formed from mono- or
bis(phosphine) gold(I) chloride complexes through the making and breaking of Au-P bonds. Reaction be-
tween the oxidized, deprotonated form of the ligand, [(P(S)Ph2)2CCN]¯, and [AuCl(PPh3)] (molar ratio 1:1)
formed the neutral mononuclear complex [Au(PPh3)(P(S)Ph2)2CCN] 3, with the [AuPPh3]+ fragment bonded
to one sulfur atom and a large degree of electron delocalization across the S-P-C-P-S ring. Complexes 1–3
were all obtained in satisfactory yield (70-90%), and analyzed by single crystal X-ray studies, solution 1H
and 31P NMR, IR, and elemental analyses.
Received 9 September 2011
Accepted 21 October 2011
Available online 29 October 2011
Keywords:
Gold(I) complexes
bis(diphenylphosphino)acetonitrile
Pentafluorophenyl
Dinuclear
X-ray crystal structures
© 2011 Elsevier B.V. All rights reserved.
Mono- and bis-tertiary phosphines are amongst the most utilized
ligands in inorganic and organometallic chemistry [1] and have been
studied in abundance in gold chemistry as well [2]. Within the bis(phos-
phine) family, the single methylene-bridged derivative, Ph2PCH2PPh2
(dppm) is an important ligand in metal coordination chemistry [3]
and derivations thereof, most notably bis-(diphenylphosphino)amine,
Ph2PNHPPh2 (dppa), have been reviewed [4]. In general, interest into
the study of these ligands stems from their use in homogeneous cataly-
sis; in particular, the rich photochemistry that emanates from gold(I)
complexes are an ongoing basis for investigation [5].
The bis(diphenylphosphino)acetonitrile, (PPh2)2CHCN, (“dppm-CN”)
ligand has been reported in the literature as the anion [(PPh2)2CCN]¯ in
a phosphorus-organic synthesis [6] and also as an anionic ligand in a se-
ries of heterometallic Ru/Au and Mn/Au complexes [7]. More recently,
this work was extended to the diphosphinoketenimine type ligand,
(PPh2)2C=C=NR [8]. Interest in the chemistry of dppm-CN was
rejuvenated by Erker and co-workers who reported the facile preparation
thereof [9], and developed diverse and fascinating aspects of its chemistry
[10]. Perhaps the most interesting is the observed sharp increase in acidity
when the H atom is replaced by a CN group on the bridging carbon
atom of dppm [11]. We prepared dppm-CN from a slight modification
of the above literature procedure [12] and recently reported the
solid-state structures of the Group 11 complexes [Au2Cl2(dppm-CN)]
and [Cu{P(O)Ph2)2CCN}2], using the dppm-CN ligand [13].
In continuing our interest in gold(I) complexes with P/S type ligands
[14], we report on new gold(I) complexes of dppm-CN utilized as a neu-
tral, anionic and oxidized ligand. The complex [(AuC6F5)2(dppm-CN)],
1, was obtained in a CH2Cl2 solution from the reaction between
dppm-CN and [AuC6F5(tht)] (molar ratio 1:2) [15]. The solution 31P
NMR spectrum of 1 showed a singlet peak resonating at δ=42.0 ppm
for the two equivalent P atoms. In the solid-state, complex 1 formed
an open-ended complex in a cis configuration and contains intramolecu-
lar Au···Au interactions, see below. The crystal structure of 1 (triclinic)
shows no packing resemblance to the previously reported structure
(monoclinic) of the closely related [(AuC6F5)2dppm] complex [16]. Al-
though both complexes contain intramolecular Au···Au interactions in
the solid-state, complex 1 additionally contains a crystal structure
motif that is unorthodox and deserves comment: Dinuclear gold(I) com-
plexes based on bis(phosphine) ligands fall into a number of observed
structural motifs [17] as summarized in Chart 1: no Au···Au interaction
A, intramolecular Au···Au interaction but without intermolecular
Au···Au interaction B, 1-D polymeric chains C (all Au···Au distances
approximately the same), and dimer type structures, D. Whereas D rep-
resents discrete “face-on” dimers [18], complex 1 shows a different
structural motif which can be described as “side-by-side” dimers along
a linear chain, depicted by E. Complex 1 shows intramolecular Au···Au
interactions are present at 3.0902(7) and 3.0809(6) Å, but each dinuclear
⁎
Corresponding author. Tel.: +27 31 260 3188; fax: +27 31 260 3091.
E-mail address: vanzylw@ukzn.ac.za (W.E. van Zyl).
1387-7003/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2011.10.030

S.V. Sithole et al. / Inorganic Chemistry Communications 15 (2012) 216–220
217
Chart 1. Shows relevant inter- and intramolecular Au···Au interactions to indicate “dimer” units within the crystal structure of E, all distances shown in angstrom.
unit is separated from each other at a distance of 3.53 Å. Whether this
borderline distance constitute a weak intermolecular Au···Au interac-
tion or not is ambiguous [19], but it is certainly longer than the norm
for an intermolecular Au···Au interaction and we therefore describe it
as having no such Au···Au interaction. In a recent critical review on aur-
ophilicity, Schmidbaur and Schier commented: “…gold(I) centres con-
tained within a given molecule, …were found to be drawn together to
intra- or intermolecular equilibrium distances in the range from ca.
2.50–3.50 Å, well below the sum of two van der Waals radii (3.80 Å),
…” [20]. Nevertheless, with a distance of only 3.53 Å between the dinuc-
lear units in 1, we describe them as dimer pairings since the next set of
dimers are well separated by more than 6.2 Å. We thus see a difference
between 1 (as represented by motif E) and B and summarize it as fol-
lows: In B, the adjacent dinuclear units are i) typically much further
away (>4 Å) so that the absence of any interaction is beyond dispute,
ii) at approximately a similar distance away, and iii) not distinctly direc-
tional. In E, the adjacent dinuclear units are i) much closer to what could
be considered an interaction, ii) at markedly different distances away
(3.53 and 6.2 Å, respectively), and iii) linearly directional.
related, complexes such as 1, which contains three well separated inter-
actions, could reveal interesting luminescence properties.
The complex [Au2{(PPh2)2CCN}2], 2, was prepared from the reac-
tion between the anion [(PPh2)2CCN]¯ and [AuCl(tht)] (molar ratio
1:1) [21]. The synthetic methodology for complexes 1–3 are shown
in Scheme 1. The yield of complex 2 was found to be significantly
higher (92%) by prolonged stirring (>30 mins) when compared
with shorter stirring times (b50% yield, 3–5 min stirring) in CH2Cl2
during the extraction step. The solution 31P NMR spectrum of 2
showed a singlet peak resonating at δ=42.8 ppm assigned to the P
atoms. Complex 2 can also be prepared from the reaction between
Li[(PPh2)2CCN] and [AuCl(PPh3)] (molar ratio 1:1) leading to substi-
tution of a neutral phosphine. The [AuPPh3]+ fragment did not re-
place the isolobal H+ proton to form neutral [(PPh2)2 C(AuPPh3)
(CN)]. Changing the gold(I) starting material from PPh3 to bis(phos-
phine) ligands (i.e. dppm or dppe) did not change the product out-
come and also formed only complex 2. Presumably the CN group
delocalizes the charge more evenly between the P atoms. Complex
2 has no intermolecular Au···Au interactions, but has short intramo-
lecular Au···Au interactions of 2.8650(4) Å. The 8-membered metal-
lacycle is in an elongated chair conformation, and both Au-P bond
lengths are approximately equal at 2.31 Å and the P–Au–P moieties
are slightly distorted from linearity at 174°. The structure is shown
in Fig. 2. Dinuclear gold(I) complexes with bridging neutral bis(phos-
phine)s ligands do not generally replace anionic bis(phosphine)s
whilst retaining dinuclearity. Instead, the opposite reaction is
readily observed in complexes of the type [AuS2PR(OR′)]2, where
̅
Complex 1 crystallized in triclinic space group P1 (Z=4) and has two
independent molecules in the asymmetric unit with an inversion as sole
symmetry operator. Within the unit cell, the inversion centre is located
between the molecules diagonally opposite the two molecules shown
in Fig. 1; and not located between the atoms labeled Au(1A) and Au
(1B). There are no features of notable importance between the molecules
related by crystallographic symmetry, the Au atoms are >15 Å apart.
Since intermolecular Au···Au distances and emission wavelengths are

218
S.V. Sithole et al. / Inorganic Chemistry Communications 15 (2012) 216–220
A
B
Fig. 1. Above: molecular structure (ORTEP) of 1 with 50% probability ellipsoids. H
atoms are removed for clarity. Atoms labeled Au(1A) and Au(1B) are not related by in-
version (see text). Selected interatomic distances (Å) and angles (°): Au(1A)–Au(2A)
3.0902, Au(1B)–Au(2B) 3.0809, Au(1A)–Au(1B) 3.529, Au(1A)–P(1A) 2.271; P(1)–Au
(1)–CF 173.2, P(1B)–C–P(2B) 112.2. Below: molecular structure of 1 showing cyano N
atom in a position to coordinate to other metal centers.
Scheme 1. Synthesis routes to neutral open-ended and cyclic mono- and dinuclear gold
(I) complexes 1–3 utilizing the dppm-CN ligand.
the ligand [S2PR(OR')]¯, which contains a ‘soft’ sulfur atom and is
anionic, can be substituted by neutral bis(phosphines) [22]. Cat-
ionic [Au2(μ-dppm)2]2+ complexes can also be deprotonated leading
to related neutral [Au2(Ph2P-X-PPh2)2] (X=N [23], CH [24]) type
complexes, and electron density on the bridging C atom can induce fur-
ther reactivity [25]. Ruiz and co-workers demonstrated that anion
[(PPh2)2CCN]¯ can be used as a chelating ligand in neutral octahedral
Mn(I) and Ru(II) complexes. These complexes react with [AuPPh3]+
and the Au center binds to the cyano N atom in both cases, and conse-
quently changes the bimetallic complexes to cationic [7].
The complex [Au(PPh3)(P(S)Ph2)2CCN], 3, was prepared from the
reaction between [(P(S)Ph2)2CCN]¯ and [AuCl(PPh3)] (molar ratio
1:1) [26]. Although a number of gold(I/III) complexes had been
reported from dppm-S2 or dppa-S2 type ligands, they are all restricted
to organogold or halogold centers attached to the sulfur atom [27].
We are unaware of reports where a [AuPR3]+ specie is attached to
sulfur in a dppmS2 or dppaS2 type derivative. The interesting gold
(III) complex [Au(C6F5)3(P(S)Ph2)2 C(AuPPh3)2] had been described
where the sulfur atom occupies the vacant coordination site of the
square planar AuIII(C6F5)3 center [28]. The solution 31P NMR spec-
trum of 3 showed a singlet peak resonating at δ=35.9 assigned to
PPh3, and a singlet peak at δ=41.1 assigned to the two P atoms in
Fig. 2. Molecular structure (ORTEP) of 2 with 50% probability ellipsoids. Selected intera-
tomic distances (Å) and angles (°): Au(1)–Au(1A) 2.8650, Au(1)–P(1) 2.3146, Au(1)–P
(2) 2.3185; P(1)–Au(1)–P(2) 174.29, Au(1)–P(1)–CCN 115.00, P(1)–C–P(2A) 119.5.

S.V. Sithole et al. / Inorganic Chemistry Communications 15 (2012) 216–220
219
References
[1] (a) F.A. Cotton, G. Wilkinson, C.A. Murillo, M. Bochmann, Advanced Inorganic
Chemistry, 6th ed. Wiley & Sons, New York, 1999;
(b) R.H. Crabtree, The Organometallic Chemistry of the Transition Metals, 3 rd
ed. Wiley & Sons, New York, 2001;
(c) J. Tsuji, Transition Metal Reagents and Catalysts, Wiley & Sons, New York,
2000;
(d) F.A. Cotton, B. Hong, Prog. Inorg. Chem. 40 (1992) 179–289;
(e) L.D. Quin, A Guide to Organophosphorus Chemistry, Wiley & Sons, New York,
2000, pp. 44–94;
(f) F.R. Hartley (Ed.), The Chemisty of Organophosphorus Compounds, vol. 1,
Wiley & Sons, New York, 1990.
[2] A. Laguna, Gold Compounds of Phosphorus and the Heavy Group V Elements, in:
H. Schmidbaur (Ed.), Gold: Progress in Chemistry, Biochemistry and Technology,
Wiley, 1999, pp. 349–427.
[3] (a) See for example:R.J. Puddephatt, Chem. Soc. Rev. 12 (1983) 99–127;
(b) D.M.A. Minahan, W.E. Hill, Coord. Chem. Rev. 55 (1984) 31–54.
[4] T. Appleby, J.D. Woollins, Coord. Chem. Rev. 235 (2002) 121–140.
[5] (a) See for example:V.W.-W. Yam, E.C.-C. Cheng, Top. Curr. Chem. 281 (2007)
269–309;
(b) V.W.-W. Yam, E.C.-C. Cheng, Chem. Soc. Rev. 37 (2008) 1806–1813;
(c) C.-M. Che, S.-W. Lai, Coord. Chem. Rev. 249 (2005) 1296–1309.
[6] A. Schmidpeter, G. Burget, Angew. Chem. Int. Ed. Engl. 24 (1985) 580–581.
[7] (a) J. Ruiz, V. Riera, M. Vivanco, S. García-Granda, M.A. Salvadó, Organometallics
15 (1996) 1079–1081;
Fig. 3. Molecular structure (ORTEP) of 3 with 50% probability ellipsoids. Selected intera-
tomic distances (Å) and angles (°): Au(1)–S(1) 2.3206, Au(1)–P(3) 2.2521, S(1)–P(1)
2.0342, P(2)–(2) 1.9720, Au(1)···S(2) 2.98; S(1)–Au(1)–P(3) 161.80, Au(1)–S(1)–P(1)
101.24, P(1)–C–P(2) 124.0.
(b) M.E.G. Mosquera, J. Ruiz, V. Riera, S. García-Granda, M.R. Díaz, C. Bois, Organ-
ometallics 20 (2001) 3821–3824.
[8] J. Ruiz, M.P. Gonzalo, M. Vivanco, R. Quesada, M.E.G. Mosquera, Dalton Trans.
(2009) 9280–9290.
[9] L. Braun, P. Liptau, G. Kehr, J. Ugolotti, R. Fröhlich, G. Erker, Dalton Trans. (2007)
1409–1415.
[10] (a) L. Braun, G. Kehr, T. Blömker, R. Fröhlich, G. Erker, Eur. J. Inorg. Chem. (2007)
3083–3090;
the dppm-CN ligand. It would appear that as the ligand becomes
more delocalized in going from 1 to 2 to 3, there is a slight but consis-
tent downfield shift of the peaks assigned to the P atoms in dppm-CN.
Complex 3 crystallized with two CH2Cl2 solvate molecules and con-
tains no intermolecular Au···Au interactions. The P-Au-S bond
angle is significantly distorted from linearity at 161° with the Au
(b) K. Spannhoff, G. Kehr, S. Kehr, R. Fröhlich, G. Erker, Dalton Trans. (2008)
3339–3344;
(c) L. Braun, G. Kehr, R. Fröhlich, G. Erker, Inorg. Chim. Acta 361 (2008)
1668–1675.
[11] K. Spannhoff, N. Kuhl, G. Kehr, R. Fröhlich, G. Erker, J. Am. Chem. Soc. 131 (2009)
17836–17842.
[12] Preparation of dppm-CN: A Schlenk tube was equipped with a magnetic stirrer bar
and THF (10 mL) was added. Dry acetonitrile (0.21 mL, 4 mmol, 1 equiv.) was
added and the tube cooled to −78 °C followed by addition of 1.6 M n-BuLi
(5 mL, 8 mmol, 2 equiv.) over 10 mins and stirred for an additional 30 mins
after which the solution turned pale yellow. Chlorodiphenylphosphine (ClPPh2)
(1.48 mL, 8 mmol, 2 equiv.) was slowly added to the cold solution which turned
the solution color red. The solution was stirred at −78 °C for a period of 15 mi-
nutes and then allowed to warm up to room temperature. All solvent was re-
moved under reduced pressure. The solid was extracted with CH2Cl2 and
filtered over a Celite/ anhydrous MgSO4 composite to remove LiCl and any
water traces, followed by 2×15 mL CH2Cl2 washings. The solvent of the filtrate
was removed under reduced pressure and dried. The residue was recrystallized
from ethanol. Yield: 1.45 g, (89 %). Mp: 138 °C (142 °C literature). The product
was used without further purification.
atom directed towards the opposite non-coordinating
S atom
(Au···S=2.98 Å). The Au-bound S-P bond length is 2.0342 Å, whilst
the terminal S-P bond length is 1.9720 Å. The structure is shown in
Fig. 3. When compared with the P4S10 molecule which contains au-
thentic double P=S (1.91 Å) and single P–S (2.10 Å) bond character,
it can be deduced that the marginal change in P-S bond length in 3,
averaging at a bond order of approximately 1.5, implies significant
electron delocalization within the S–P–C–P–S ring. X-ray crystal
data for 1–3 are reported in [29].
In summary, we have prepared and structurally characterized
three new neutral mono- or dinuclear gold(I) complexes starting
with the neutral, anionic or oxidized dppm-CN ligand. Substituting a
proton on the bridging carbon atom with a cyano group could lead
to significant differences in structure compared to more commonly
used dppm and dppa ligands. Further investigations into the reactiv-
ity of these complexes are in progress.
[13] (a) S.V. Sithole, R.J. Staples, W.E. van Zyl, Acta Cryst. E67 (2011) m64;
(b) S.V. Sithole, R.J. Staples, W.E. van Zyl, Acta Cryst. E67 (2011) m1217.
[14] (a) W.E. van Zyl, R.J. Staples, J.P. Fackler Jr., Inorg. Chem. Commun. 1 (1998)
51–54;
(b) W.E. van Zyl, J.M. López-de-Luzuriaga, A.A. Mohamed, R.J. Staples, J.P. Fackler
Jr., Inorg. Chem. 41 (2002) 4579–4589;
(c) W.E. van Zyl, Comments Inorg. Chem. 31 (2010) 13–45.
[15] Preparation of 1: In a Schlenk tube, a CH2Cl2 (10 mL) solution of [AuC6F5(tht)]
(220 mg, 0.48 mmol, 2 equiv) was slowly added to a CH2Cl2 (3 mL) solution of
dppm-CN (101 mg, 0.24 mmol) and the mixture stirred for 30 mins, followed
by complete removal of solvent and tht under reduced pressure. The product was
obtained as a free flowing pale-yellow powder. Yield (227 mg, 0.20 mmol) 83%. Mp:
115–117 °C (decompose). Elemental analysis for complex C38H21Au2F10NP2 Found:
C, 39.94, H, 2.11, N, 1.12, requires C, 40.13, H 1.86, N 1.23. 1H NMR (400 MHz, CDCl3,
298 K) δH=7.88-7.82 (m, 20H, Ph), 4.71 (t, 1H; CH, 1JP,H =10.85 Hz); 31P NMR
(101 MHz, CDCl3, 298 K) δP=42.0 (s, 2P). IR (KBr, cm-1): ν(CN) 2137. ESI-MS: m/z
1138 [M+]. Single X-ray quality crystals were obtained by layering hexane onto a
CH2Cl2 solution.
[16] P.G. Jones, C. Thöne, Acta Cryst. C48 (1992) 1312–1314.
[17] P.M. Van Calcar, M.M. Olmstead, A.L. Balch, Inorg. Chem. 36 (1997) 5231–5238.
[18] (a) P.A. Bates, J.M. Waters, Inorg. Chim. Acta 98 (1985) 125–129;
(b) D.S. Eggleston, D.F. Chodosh, G.R. Girard, D.T. Hill, Inorg. Chim. Acta 108
(1985) 221–226.
Acknowledgments
WEvZ gratefully acknowledges financial support from the University
of KwaZulu-Natal, as well as Rand Refineries (South Africa) for a gift of
gold salt. SVS thanks the National Research Foundation (NRF) for an Inno-
vative Grant. RJS thanks Michigan State University where the CCD-based
X-ray diffractometer was upgraded and/or replaced by departmental
funds.
[19] P. Pyykkö, Chem. Rev. 97 (1997) 597–636.
[20] H. Schmidbaur, A. Schier, Chem. Soc. Rev. (in press). doi:10.1039/c1cs15182g.
[21] Preparation of 2: In a Schlenk tube, a THF (10 mL) solution of dppm-CN (700 mg,
Appendix A. Supplementary material
Crystallographic data were deposited with the Cambridge
Crystallographic Data Centre (CCDC) as supplementary material
under deposition Nos. CCDC 790344, 843308 & 843309. Copies of
this material can be obtained free of charge from CCDC via www.
ccdc.cam.ac.uk/data-request/cif. or e-mail: deposit@ccdc.cam.ac.uk).
1.71 mmol,
1 equiv.) was cooled to −78 °C and n-BuLi (2.5 M, 0.70 mL,
1.71 mmol, 1 equiv.) was added dropwise. The solution was stirred for 30 mins
then [AuCl(tht)] (548 mg, 1.71 mmol) was slowly added. The resulting mixture
was stirred at −78 °C for 30 mins and then allowed to warm up to room temper-
ature and then stirred further for 10 mins. The solid was extracted with CH2Cl2
and filtered over Celite/ anhydrous MgSO4 composite to remove LiCl, followed

220
S.V. Sithole et al. / Inorganic Chemistry Communications 15 (2012) 216–220
by 2×15 mL CH2Cl2 washings. The filtrate solution was evaporated under re- temperature apparatus operating at 173 K.
A
Mo-Kα wavelength of
duced pressure leaving the product as free flowing pale-yellow powder after dry-
ing it in vacuo for a period of two hours. Yield (1.47 g, 1.21 mmol) 92%. Mp:
0.71073 Å was used. Crystals were mounted on a Nylon loop using a small
amount of paratone oil. Data were measured using omega and phi scans of
0.5° per frame for 30 s. The total number of images was based on results
from the program COSMO [30] where redundancy was expected to be 4.0
and completeness of 100% out to 0.83 Å. Cell parameters were retrieved
using APEX II software [31] and refined using SAINT on all observed reflec-
tions. Data reduction was performed using the SAINT software [32] which cor-
rects for Lp. Scaling and absorption corrections were applied using SADABS
[33] multi-scan technique, supplied by George Sheldrick. The structures
were solved by direct method using the SHELXS-97 program and refined by
least squares method on F2, SHELXL- 97, which are incorporated in
SHELXTL-PC V 6.10 [34]. All non-hydrogen atoms are refined anisotropically.
200–205 °C (decompose). Elemental analysis for complex
C52H40Au2N2P4
Found: C 51.19, H 3.18, N 2.19 requires C, 51.59; H 3.33; N, 2.31. 1H NMR
(400 MHz, CDCl3, 298 K) δH=7.55-7.42 (m, 40H, 10 Ph); 31P NMR (101 MHz,
CDCl3 298 K) δP=42.8 (s). IR (KBr, cm−1): 2133 ν(CN). Single X-ray quality crys-
tals were obtained by layering hexane onto a CH2Cl2 solution.
[22] A. Maspero, I. Kani, A.A. Mohamed, M.A. Omary, R.J. Staples, J.P. Fackler Jr., Inorg.
Chem. 42 (2003) 5311–5319.
[23] H. Schmidbaur, S. Schnatterer, K.C. Dash, A.A.M. Aly, Z. Naturforsch, Teil B 38
(1983) 62.
[24] H. Schmidbaur, J.R. Mandl, Angew. Chem., Int. Ed. Engl. 16 (1977) 640–641.
[25] (a) R. Usón, A. Laguna, M. Laguna, M.C. Gimeno, P.G. Jones, C. Fittschen, G.M.
Sheldrick, J. Chem. Soc. Chem. Commun. (1986) 509–510;
Hydrogens were calculated by geometrical methods and refined as
a
riding model. The crystal used for the diffraction study showed no
(b) E.J. Fernandez, M.C. Gimeno, P.G. Jones, A. Laguna, M. Laguna, J.M. López-de-
Luzuriaga, Organometallics 14 (1995) 2918–2922;
decomposition during data collection. Crystal data for 1: C38H21Au2F10NP2;
M=1137.43 g/mol; T=173(2) K; triclinic; space group P1 (# 2);
̅
(c) E.J. Fernandez, M.C. Gimeno, P.G. Jones, A. Laguna, M. Laguna, J.M. López-de-
Luzuriaga, Angew. Chem. Intl. Ed. Engl. 33 (1994) 87–88.
a=10.3567(15) Å, b=15.125(2) Å, c=24.723(4) Å, α=76.668(2)°,
β=80.190(2)°, γ=70.970(2)°; V=3543.4(9) Å3; Z=4; Dc =2.132 mg/m3;
μ(Mo-Kα)=8.444 mm-1; F(000)=2136; 51669 reflections collected; 12896
unique; GoF on F2 =1.219; R1=0.0577, wR2=0.1770; R indices (all data)
[26] Preparation of 3: In a Schleck tube, a THF (8 mL) solution of dppm-CN(S)2 (220 mg,
0.46 mmol) was cooled to −78 °C. MeLi (0.28 ml, 0.46 ml) was added dropwise and
the resulting solution stirred for 1 hour. Separately, a THF (10 mL) solution of
[AuClPPh3] (227 mg, 0.46 mmol) was made up and slowly added to the lithiated
dppm-CN(S)2 mixture. After 30 mins at −78 °C, the solution was allowed to
warm up to room temperature and stirred for an additional 30 mins. All solvent
was then removed under reduced pressure. The product was extracted with
CH2Cl2 (20 ml) and then filtered through a Celite/ anhydrous MgSO4 composite,
followed by removal of all filtrate solvent under reduced pressure. The product
was a free flowing cream-white powder. Yield: (375 mg, 0.34 mmol) 70%; Mp:
R1=0.0668,
wR2=0.1849.
Crystal
data
for
2:
C52H40Au2N2P4;
M=1210.67 g/mol; T=173(2) K; monoclinic; space group P21/n (#14);
a=9.6667(6) Å, b=14.9403(9) Å, c=15.3179(9) Å, α=90°, β=90.1420
(10)°, γ=90°; V=2212.3(2) Å3; Z=2; Dc =1.817 mg/m3; μ(Mo-Kα)=
6.808 mm-1; F(000)=1168; 31123 reflections collected; 4058 unique; GoF
on F2=1.098; R1=0.0338, wR2=0.0903;
R indices (all data) R1=0.0350,
wR2=0.0911. Crystal data for 3: C44H35AuNP3S2·2CH2Cl2; M=1101.58 g/mol;
T=173(2) K; orthorhombic; space group Pca21 (#29); a=17.6668(10) Å,
b=14.3187(8) Å, c=18.1931(11) Å, α=β=γ=90°; V=4602.2(5) Å3; Z=4;
Dc=1.590 mg/m3; μ(Mo-Kα)=3.657 mm-1; F(000)=2184; 42736 reflections col-
lected; 11091 unique; GoF on F2=1.005; R1=0.0293, wR2=0.0667; R indices (all
data) R1=0.0394, wR2=0.
105–107 °C; Elemental analysis for complex
C44H35AuNP3S2·2CH2Cl2 found:
C 49.9, H 4.16 N 1.19 requires: C 50.1, H 3.57 N 1.27; 1H NMR (400 MHz, CDCl3,
298 K) δH=7.87-7.23 (m, 35H, Ph); 13 C NMR (101 MHz, CDCl3, 298 K) δC=133.9,
132.2, 131.1, 128.8, 128.7, 128.2, 125.1 31P NMR (101 MHz, CDCl3, 298 K) δP=35.9
(s, 1P, PPh3), 41.1 [s, 2P, PPh2 (dppm-CN)]. IR (ATR, cm-1): ν(CN) 2243, ν(Ph-P)
1432, ν(P=S) 743–658. Single X-ray quality crystals were obtained by layering
hexane onto a CH2Cl2 solution.
[30] COSMO V1.58, Software for the CCD Detector Systems for Determining Data Col-
lection Parameters, Bruker Analytical X-ray Systems, Madison, WI, 2008.
[31] APEX2 V2008.5-0 Software for the CCD Detector System, Bruker Analytical X-ray
Systems, Madison, WI, 2008.
[27] (a) A. Laguna, M. Laguna, A. Rojo, M.N. Fraile, J. Organomet. Chem. 315 (1986) 269;
(b) A. Laguna, M. Laguna, M.N. Fraile, E. Fernandez, P.G. Jones, Inorg. Chim. Acta
150 (1988) 233–236;
[32] SAINT
V 7.34 Software for the Integration of CCD Detector System Bruker
Analytical X-ray Systems, Madison, WI , 2008.
(c) A. Laguna, M. Laguna, J. Organomet. Chem. 394 (1990) 743–756.
[28] B. Alvarez, E.J. Fernandez, M.C. Gimeno, P.G. Jones, A. Laguna, J.M. Lopez-de-Luzuriaga,
Polyhedron 17 (1998) 2029–2035.
[33] (a) SADABS V2.008/2 Program for absorption corrections using Bruker-AXS CCD.
(b) R.H. Blessing, Acta Cryst. A51 (1995) 33–38.
[34] G.M. Sheldrick, Acta Cryst. A64 (2008) 112–122.
[29] The X-ray diffraction data of the complexes 1–3 were collected using a Bruker
Smart APEX II CCD diffractometer equipped with an Oxford Cryostream low-