Preparation of diethylcyanamide and cyanoguanidine complexes of manganese and rhenium

Article abstract of DOI:10.1016/j.jorganchem.2014.05.028

Diethycyanamide complexes [M(NCNEt₂)(CO)_nL _5-n]BPh₄ (1a-5a) [M = Mn, Re; n = 1, 2, 3; L = PPh(OEt)₂, P(OEt)₃] were prepared by allowing hydrides MH(CO)_nL_5-n to react f

Full text of DOI:10.1016/j.jorganchem.2014.05.028

Accepted Manuscript
Preparation of Diethylcyanamide and Cyanoguanidine Complexes of Manganese and
Rhenium
Gabriele Albertin , Stefano Antoniutti , Jesús Castro , Silvio Siddi
PII:
S0022-328X(14)00265-4
10.1016/j.jorganchem.2014.05.028
JOM 18600
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 11 April 2014
Revised Date: 16 May 2014
Accepted Date: 22 May 2014
Please cite this article as: G. Albertin, S. Antoniutti, J. Castro, S. Siddi, Preparation of Diethylcyanamide
and Cyanoguanidine Complexes of Manganese and Rhenium, Journal of Organometallic Chemistry
(2014), doi: 10.1016/j.jorganchem.2014.05.028.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
> Synthesis of diethylcyanamide and cyanoguanidine complexes of manganese and rhenium.
> The first bis(diethylcyanamide) complexes of manganese and rhenium were also prepared.
> Crystallographic characterization of two complexes is described.
1

ACCEPTED MANUSCRIPT
Preparation of Diethylcyanamide and Cyanoguanidine Complexes of Manganese and
Rhenium
Gabriele Albertin,a* Stefano Antoniutti,a Jesús Castro,b Silvio Siddia
a Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia, Dorsoduro
2137, 30123 Venezia, Italy.
b Departamento de Química Inorgánica, Universidade de Vigo, Facultade de Química, Edificio de
Ciencias Experimentais, 36310 Vigo (Galicia), Spain.
* Corresponding author. Fax: +390412348594, email: albertin@unive.it
A B S T R A C T
Diethycyanamide complexes [M(N≡CNEt2)(CO)nL5-n]BPh4 (1a–5a) [M = Mn, Re; n = 1, 2,
3; L = PPh(OEt)2, P(OEt)3] were prepared by allowing hydrides MH(CO)nL5-n to react first with
triflic acid (HOTf) and then with an excess of diethylcyanamide. The related cyanoguanidine
derivatives [M{N≡CN(H)C(NH2)=NH}(CO)nL5-n]BPh4 (1b–4b) were prepared by reacting hydrides
MH(CO)nL5-n first with an equivalent of HOTf and then with an excess of cyanamide N≡CNH2 or,
alternatively, with cyanoguanidine. Bis(diethylcyanamide) complexes MBr(N≡CNEt2)2(CO)3 (6, 7)
were prepared by allowing pentacarbonyl species MBr(CO)5 to react with an excess of cyanamide
N≡CNEt2. The complexes were characterised by spectroscopy (IR, 1H, 31P, 13C NMR) and by X-ray
crystal structure determination of [Mn(N≡CNEt2)(CO)2{PPh(OEt)2}3]BPh4 (2a) and
ReBr(N≡CNEt2)2(CO)3 (7a).
Keywords: Manganese; Rhenium; Diethylcyanamide; Cyanoguanidine; Synthesis
1. Introduction
The synthesis and reactivity of transition metal complexes containing cyanamide N≡CNR2
(R = H, alkyl, aryl) or its dimeric form, cyanoguanidine N≡CN(H)C(NH2)=NH, as ligands has been
relatively little developed over the years [1-8], in spite of the close relationship with the nitrile RCN
complexes [9] and the biological and synthetic interest [10] of these amino-functionalised nitrile
species. Only a limited number of cyanamide and cyanoguanidine complexes of transition metals
have been reported, mainly with molybdenum [7], platinum [6] or copper [5] as central metals.
1

ACCEPTED MANUSCRIPT
Instead, only two papers give reports for both manganese [11] and rhenium [12], involving Mn(η5-
C5H5)(CO)2(N≡CNEt2) and ReCl2(N≡CNEt2)(PMePh2)3 derivatives, respectively.
We are interested in the chemistry not only of “diazo” complexes of transition metals with d6
configuration [13], but also of nitrile derivatives [14] and, recently, diethylcyanamide and
cyanoguanidine complexes of ruthenium and osmium [15]. We have now extended these studies on
cyanamide derivatives to the manganese triad, and this paper reports the synthesis of the first
cyanoguanidine and bis(diethylcyanamide) complexes of manganese and rhenium.
2. Experimental section
2.1. General comments
All reactions were carried out in an inert atmosphere (argon) by means of standard Schlenk
techniques or in an inert-atmosphere glove box. Once isolated, the complexes were found to be
relatively stable in air. All solvents were dried over appropriate drying agents, degassed on a
vacuum line, and distilled into vacuum-tight storage flasks. Mn2(CO)10 and Re2(CO)10 were
Pressure Chemical Co. (USA) products, used as received. The phosphane PPh(OEt) was prepared
2
by the method of Rabinowitz and Pellon [16], whereas triethoxyphosphane P(OEt)3 was an Aldrich
product, purified by distillation under nitrogen. Other reagents were purchased from commercial
sources in the highest available purity and used as received. Infrared spectra were recorded on a
Perkin-Elmer Spectrum-One FT-IR spectrophotometer. NMR spectra (1H, 31P, 13C) were obtained
on an AVANCE 300 Bruker spectrometer at temperatures between -90 and +30 °C, unless
otherwise noted. 1H and 13C{1H} spectra are referred to internal tetramethylsilane; 31P{1H}
chemical shifts are reported with respect to 85% H3PO4; downfield shifts are considered positive.
COSY, HMQC and HMBC NMR experiments were performed with standard programs. The iNMR
software package [17] was used to process NMR data. The conductivity of 10-3 mol dm-3 solutions
of the complexes in CH3NO2 at 25 °C was measured on a Radiometer CDM 83. Elemental analyses
were determined in the Microanalytical Laboratory of the Dipartimento di Scienze del Farmaco,
University of Padova (Italy).
2.2. Synthesis of complexes
Hydrides MnH(CO)nL5-n (n = 3, 2, 1) and ReH(CO)nL5-n (n = 3, 2) [L = P(OEt)3, PPh(OEt)2]
were prepared following the previously reported methods [18,19].
2

ACCEPTED MANUSCRIPT
2.2.1. [Mn(N
≡CNEt2)(CO)nL5-n]BPh4 (1a–3a) [n = 3 (1a), 2 (2a), 1 (3a); L = PPh(OEt)2]
A slight excess of triflic acid HOSO2CF3 (HOTf) (0.22 mmol, 20 µL) was added to a solution
of the appropriate hydride MnH(CO)nL5-n (0.20 mmol) in 8 mL of CH2Cl2 cooled to -196 °C. The
reaction mixture was allowed to reach the room temperature, stirred for 1 h, and then an excess of
diethylcyanamide N≡CNEt2 (0.8 mmol, 93 µL) added. After 3 h of stirring, the solvent was
removed under reduced pressure to give an oil, which was triturated with ethanol (2 mL) containing
an excess of NaBPh4 (0.28 mmol, 96 mg). A yellow solid slowly separated out from the resulting
solution cooled to -25 °C, which was filtered and crystallised from ethanol; yield 0.137 g (72%) for
1a, 0.177 g (79%) for 2a, 0.220 g (85%) for 3a.
1a: IR (KBr pellet) νCN: 2258 (m); νCO: 2062 (w), 1987, 1947 (s) cm-1. 1H NMR (CD2Cl2,
20 °C) δ: 7.65–6.89 (m, 30 H, Ph), 4.11, 4.01 (m, 8 H, CH2 phos), 2.42 (q, 4 H, CH2 cyanamide),
1.42 (t, 12 H, CH3 phos), 0.80 (t, 6 H, CH3 cyanamide) ppm. 31P{1H} NMR (CD2Cl2, 20 °C) δ: A2
spin syst, 190.5 (s br); (CD2Cl2, -70 °C): δ = (A2 spin syst) 191.1 (s) ppm. ΛM = 51.8 ꢀ-1 mol-1 cm2.
C52H60N2BMnO7P2 (952.74): calcd. C 65.55, H 6.35, N 2.94; found C 65.37, H 6.42, N 3.03%.
2a: IR (KBr pellet) νCN: 2253 (m); νCO: 1978, 1897 (s) cm-1. 1H NMR (CD2Cl2, 20 °C) δ:
7.60–6.88 (m, 35 H, Ph), 4.15–3.75 (m, 12 H, CH2 phos), 2.36 (q, 4 H, CH2 cyanamide), 1.37, 1.35,
1.34 (t, 18 H, CH3 phos), 0.80 (t, 6 H, CH3 cyanamide) ppm. 31P{1H} NMR (CD2Cl2, -70 °C) δ:
A2B spin syst, δA 197.3, δB 182.0, JAB = 62.0 Hz. ΛM = 55.1 ꢀ-1 mol-1 cm2. C61H75N2BMnO8P3
(1122.93): calcd. C 65.24, H 6.73, N 2.49; found C 65.05, H 6.59, N 2.41%.
3a: IR (KBr pellet) νCN: 2253 (m); νCO: 1880 (s) cm-1. 1H NMR (CD2Cl2, 20 °C) δ: 7.58–6.88
(m, 40 H, Ph), 3.63 (m, 16 H, CH2 phos), 2.77 (q, 4 H, CH2 cyanamide), 1.18 (t, 24 H, CH3 phos),
1.04 (t, 6 H, CH3 cyanamide) ppm. 31P{1H} NMR (CD2Cl2, 20 °C) δ: A4 spin syst, 200.0 (br);
(CD2Cl2, -70 °C): δ = (A4 spin syst) 197.2 (s br) ppm. ΛM = 55.6 ꢀ-1 mol-1 cm2. C70H90N2BMnO9P4
(1293.12): calcd. C 65.02, H 7.02, N 2.17; found C 64.84, H 7.16, N 2.06%.
2.2.2. [Mn{N≡CN(H)C(NH2)=NH}(CO)nL5-n]BPh4 (1b, 2b) [n = 3 (1b), 2 (2b); L = PPh(OEt)2]
Method 1: A slight excess of HOTf (0.22 mmol, 20 µL) was added to a solution of the
appropriate hydride MnH(CO)nL5-n (0.20 mmol) in 8 mL of toluene cooled to -196 °C and the
reaction mixture, brought to room temperature, was stirred for 1 h. An excess of cyanamide
N≡CNH2 (0.8 mmol, 34 mg) in ethanol (5 mL) was added and the resulting mixture stirred for 24 h.
3

ACCEPTED MANUSCRIPT
The solvent was removed under reduced pressure to give an oil, which was triturated with ethanol
(2 mL) containing an excess of NaBPh4 (0.4 mmol, 137 mg). A white solid slowly separated out by
cooling the resulting solution to -25 °C, which was filtered and crystallised from dichloromethane
and ethanol; yield 0.122 g (65%) for 1b, 0.133 g (60%) for 2b.
Method 2: A An excess of HOTf (0.22 mmol, 20 µL) was added to a solution of the
appropriate hydride MnH(CO)nL5-n (0.20 mmol) in 8 mL of toluene cooled to -196 °C and the
reaction mixture, brought to room temperature, was stirred for 1 h. An excess of cyanoguanidine
N≡CN(H)C(NH2)=NH (0.4 mmol, 34 mg) in ethanol (5 mL) was added and the resulting mixture
stirred for 24 h. The solvent was removed under reduced pressure to give an oil, which was treated
with ethanol (2 mL) containing an excess of NaBPh4 (0.4 mmol, 137 mg). A white solid slowly
separated out by cooling the resulting solution to -25 °C, which was filtered and crystallised from
dichloromethane and ethanol; yield 0.143 g (76%) for 1b, 0.164 g (74%) for 2b.
1b: IR (KBr pellet) νNH: 3456, 3407, 3326 (m); νCN: 2237 (m); νCO: 2059 (m), 1972, 1942 (s);
δNH : 1632 (s) cm-1. 1H NMR (CD2Cl2, 20 °C) δ: 7.65–6.89 (m, 30 H, Ph), 4.06, 3.96 (m, 8 H, CH2),
2
3.51 (s br, 4 H, NH+NH2 cyanamide), 1.38 (t, 12 H, CH3); (CD2Cl2, -70 °C): δ = 7.55–6.89 (m br,
30 H, Ph), 3.96, 3.84 (br, 8 H, CH2), 3.09, 2.29 (br, 4 H, NH+NH2 cyanamide), 1.29 (t br, 12 H,
CH3) ppm. 31P{1H} NMR (CD2Cl2, 20 °C) δ: A2 spin syst, 189.5 (s br); (CD2Cl2, -70 °C): δ = (A2
spin syst) 189.6 (s) ppm. ΛM = 53.2 ꢀ-1 mol-1 cm2. C49H54N4BMnO7P2 (938.67): calcd. C 62.70, H
5.80, N 5.97; found C 62.58, H 5.92, N 6.11%.
2b: IR (KBr pellet) νNH: 3502 (w), 3439, 3389, 3367 (m); νCN: 2247 (m); νCO: 1967, 1903 (s);
δNH : 1623 (s) cm-1. 1H NMR (CD2Cl2, 20 °C) δ: 7.50–6.88 (m, 35 H, Ph), 3.96, 3.83, 3.73, 3.67 (m,
2
12 H, CH2), 3.47 (s br, 4 H, NH+NH2 cyanamide), 1.32, 1.31, 1.27 (t, 18 H, CH3); (CD2Cl2,
-70 °C): δ = 3.55, 2.13 (br, 4 H, NH+NH2 cyanamide) ppm. 13C{1H} NMR (CD2Cl2, 20 °C) δ:
222.1, 219.6 (m br, CO), 165–122 (m, Ph), 63.10 (m, CH2), 58.6 (s, C=NH), 16.48 (m, CH3) ppm.
31P{1H} NMR (CD2Cl2, -70 °C) δ: A2B spin syst, δA 195.7, δB 182.8, JAB = 58.3 Hz. ΛM = 52.7 ꢀ-1
mol-1 cm2. C58H69N4BMnO8P3 (1108.86): calcd. C 62.82, H 6.27, N 5.05; found C 63.00, H 6.17, N
4.96%.
2.2.3. [Re(N≡CNEt2)(CO)3{PPh(OEt)2}2]BPh4 (4a) and [Re(N≡CNEt2)(CO)2{P(OEt)3}3]BPh4 (5a)
A slight excess of HOTf (0.165 mmol, 15 µL) was added to a solution of the appropriate
hydride ReH(CO)nL5-n (0.15 mmol) in 8 mL of CH2Cl2 cooled to -196 °C and the reaction mixture,
4

ACCEPTED MANUSCRIPT
brought to room temperature, was stirred for 1 h. An excess of diethylcyanamide N≡CNEt2 (0.75
mmol, 87 µL) was added and the reaction mixture stirred for 24 h. The solvent was removed under
reduced pressure to give an oil, which was treated with ethanol (2 mL) containing an excess of
NaBPh4 (0.3 mmol, 103 mg). A pale-yellow solid slowly separated out by cooling the resulting
solution to -25 °C, which was filtered and crystallised from ethanol; yield 0.137 g (84%) for 4a,
0.141 g (81%) for 5a.
4a: IR (KBr pellet) νCN: 2260 (m); νCO: 2068 (w), 1980, 1942 (s) cm-1. 1H NMR (CD2Cl2,
20 °C) δ: 7.65–6.88 (m, 30 H, Ph), 4.03, 3.96 (m, 8 H, CH2 phos), 2.56 (q, 4 H, CH2 cyanamide),
1.40 (t, 12 H, CH3 phos), 0.87 (t, 6 H, CH3 cyanamide) ppm. 31P{1H} NMR (CD2Cl2, 20 °C) δ: A2
spin syst, 134.8 (s br); (CD2Cl2, -70 °C): δ = (A2 spin syst) 136.25 (s) ppm. ΛM = 52.5 ꢀ-1 mol-1
cm2. C52H60N2BO7P2Re (1084.01): calcd. C 57.62, H 5.58, N 2.58; found C 57.39, H 5.46, N
2.64%.
5a: IR (KBr pellet) νCN: 2264 (m); νCO: 1905, 1892 (s) cm-1. 1H NMR (CD2Cl2, 20 °C) δ:
7.32–6.88 (m, 20 H, Ph), 4.05 (m, 18 H, CH2 phos), 3.09 (q, 4 H, CH2 cyanamide), 1.34, 1.32 (t, 27
H, CH3 phos), 1.25 (t, 6 H, CH3 cyanamide) ppm. 13C{1H} NMR (CD2Cl2, 20 °C) δ: 193.58 (td,
CO, JCP = 11.3, JCP = 2.3 Hz), 191.94 (td, CO, JCP = 80.0, JCP = 8.3 Hz), 165–122 (m, Ph), 66.04 (s,
C≡N), 62.05 (m, CH2 phos), 46.7 (s, CH2 cyanamide), 16.32 (m, CH3 phos), 13.37 (s, CH3
cyanamide) ppm. 31P{1H} NMR (CD2Cl2, -30 °C) δ: A2B spin syst, δA 115.6, δB 114.4, JAB = 47.5
Hz. ΛM = 53.0 ꢀ-1 mol-1 cm2. C49H75N2BO11P3Re (1158.07): calcd. C 50.82, H 6.53, N 2.42; found
C 50.65, H 6.63, N 2.35%.
2.2.4. [Re{N
≡CN(H)C(NH2)=NH}(CO)3{PPh(OEt)2}2]BPh4 (4b) and [Re{N≡CN(H)C(NH2)=NH}-
(CO)2{P(OEt)3}3]BPh4 (5b)
Method 1: An excess of HOTf (0.165 mmol, 15 µL) was added to a solution of the
appropriate hydride ReH(CO)nL5-n (0.20 mmol) in 8 mL of CH2Cl2 cooled to -196 °C and the
reaction mixture, brought to room temperature, was stirred for 1 h. An excess of cyanamide
N≡CNH2 (0.6 mmol, 25 mg) in ethanol (5 mL) was added and the resulting mixture stirred for 24 h.
The solvent was removed under reduced pressure to give an oil, which was triturated with ethanol
(2 mL) containing an excess of NaBPh4 (0.3 mmol, 103 mg). A pale-yellow solid slowly separated
out by cooling the resulting solution to -25 °C, which was filtered and crystallised from
dichloromethane and ethanol; yield 0.170 g (80%) for 4b, 0.195 g (85%) for 5b.
5

ACCEPTED MANUSCRIPT
Method 2: The complex was prepared exactly like with Method 1, but using cyanoguanidine
(0.3 mmol, 25 mg) as a reagent; yield 0.175 g (82%) for 4b, 0.195 g (85%) for 5b.
4b: IR (KBr pellet) νNH: 3493 (w), 3411, 3322 (m); νCN: 2240 (m); νCO: 2061 (w), 1972, 1955
(s); δNH : 1632 (s) cm-1. 1H NMR (CD2Cl2, 20 °C) δ: 7.62–6.88 (m, 30 H, Ph), 4.28 (br, 4 H,
2
NH+NH2 cyanamide), 4.06, 3.99 (m, 8 H, CH2), 1.37 (t, 12 H, CH3); (CD2Cl2, -30 °C): δ = 7.60–
6.97 (m, 30 H, Ph), 4.03, 3.88 (m br, 8 H, CH2), 3.77, 2.78 (br, 4 H, NH+NH2 cyanamide), 1.38 (t,
12 H, CH3) ppm. 31P{1H} NMR (CD2Cl2, 20 °C) δ: A2 spin syst, 134.0 (s); (CD2Cl2, -30 °C): δ =
(A2 spin syst) 134.4 (s) ppm. ΛM = 52.6 ꢀ-1 mol-1 cm2. C49H54N4BO7P2Re (1069.94): calcd. C 55.01,
H 5.09, N 5.24; found C 54.82, H 5.18, N 5.15%.
5b: IR (KBr pellet) νNH: 3529, 3440, 3344 (m); νCN: 2247 (m); νCO: 1981, 1900 (s); δNH
1634 (s) cm-1. 1H NMR (CD2Cl2, 20 °C) δ: 7.52–6.88 (m, 20 H, Ph), 4.78 (m, 4 H, NH+NH2
:
2
cyanamide), 4.12 (m, 18 H, CH2), 1.40, 1.39 (t, 27 H, CH3); (CD2Cl2, -70 °C): δ = 7.53–7.07 (m, 20
H, Ph), 4.99, 4.31 (br, 4 H, NH+NH2 cyanamide), 4.10, 3.87 (br, 18 H, CH2), 1.41, 1.39 (t, 27 H,
CH3) ppm. 31P{1H} NMR (CD2Cl2, -70 °C) δ: AB2 spin syst, δA 119.2, δB 116.5, JAB = 46.2 Hz.
ΛM = 54.4 ꢀ-1 mol-1 cm2. C46H69N4BO11P3Re (1144.00): calcd. C 48.29, H 6.08, N 4.90; found C
49.07, H 6.00, N 5.12%.
2.2.5. fac-MnBr(N≡CNEt2)2(CO)3 (6a)
An excess of diethylcyanamide (1.8 mmol, 209 µL) was added to a solution of the
pentacarbonyl complex MnBr(CO)5 (100 mg, 0.36 mmol) in toluene (8 mL) and the reaction
mixture was stirred at room temperature for 24 h. The solvent was removed under reduced pressure
to give an oil, which was triturated with ethanol (3 mL). A pale-yellow solid slowly separated out
by cooling the resulting solution to -25 °C, which was filtered and crystallised from
dichloromethane and ethanol; yield 130 mg (87%). IR (KBr pellet) νCN: 2264 (m); νCO: 2033 (m),
1930, 1910 (s) cm-1. 1H NMR (CD2Cl2, 20 °C) δ: 3.19 (q, 8 H, CH2), 1.32 (t, 12 H, CH3) ppm.
C13H20N4BrMnO3 (415.16): calcd. C 37.61, H 4.86, N 13.50; found C 37.79, H 4.75, N 13.37%.
2.2.6. fac-ReBr(N≡CNEt2)2(CO)3 (7a)
An excess of diethylcyanamide (1.23 mmol, 143 µL) was added to a solution of the
pentacarbonyl complex ReBr(CO)5 (100 mg, 0.25 mmol) in toluene (8 mL) and the reaction mixture
was refluxed for 5 h. The solvent was removed under reduced pressure to give an oil, which was
6

ACCEPTED MANUSCRIPT
triturated with ethanol (3 mL). A white solid slowly separated out by cooling the resulting solution
to -25 °C, which was filtered and crystallised from dichloromethane and ethanol; yield 116 mg
(85%). IR (KBr pellet) νCN: 2264 (m); νCO: 2023 (m), 1917, 1897 (s) cm-1. 1H NMR (CD2Cl2,
20 °C) δ: 3.17 (q, 8 H, CH2), 1.33 (t, 12 H, CH3) ppm. C13H20N4BrO3Re (546.43): calcd. C 28.57, H
3.69, N 10.25; found C 28.43, H 3.80, N 10.12%.
2.2.6. mer-cis-ReBr(N≡CNEt2)2(CO)3 (7a1)
In a 25-mL three-necked round-bottomed flask were placed 80 mg (0.15 mmol) of fac-
ReBr(N≡CNEt2)2(CO)3 (7a), an excess of NaBPh4 (0.2 mmol, 68 mg) and 10 mL of ethanol. The
reaction mixture was stirred for 2 h and then the solvent removed under reduced presure to about 2
mL. By cooling the reaction mixture to -25 °C, a pale-yellow solid separated out, which was filtered
and dried under vacuum; yield 72 mg (90%). IR (KBr pellet) νCN: 2264 (m); νCO: 2034 (w), 1928,
1872 (s) cm-1. 1H NMR (CD2Cl2, 20 °C) δ: 3.11, 3.02 (q, 8 H, CH2), 1.27, 1.23 (t, 12 H, CH3) ppm.
C13H20N4BrO3Re (546.43): calcd. C 28.57, H 3.69, N 10.25; found C 28.69, H 3.75, N 10.12%.
2.3. X-ray Crystallography
Crystallographic data were collected (at room temperature for 2a and at low temperature for
7a) on a Bruker Smart 1000 CCD diffractometer at CACTI (Universidade de Vigo) using graphite
monochromated Mo-K〈 radiation (λ = 0.71073 Å), and were corrected for Lorentz and polarisation
effects. The software SMART [20] was used for collecting frames of data, indexing reflections, and
the determination of lattice parameters, SAINT [21] for integration of intensity of reflections and
scaling, and SADABS [22] for empirical absorption correction. The crystallographic treatment was
performed with the Oscail program [23]. The structures were solved by Patterson method and
refined by a full-matrix least-squares based on F2 [24]. Non-hydrogen atoms were refined with
anisotropic displacement parameters. Hydrogen atoms were included in idealized positions and
refined with isotropic displacement parameters. The NEt2 fragment of the dialkylcyanamide groups
are usually disorder [25], so for 2a it was necessary to apply some restrains. The SADI instruction
was applied for fix C–C and C–N lengths. Details of crystal data and structural refinement are given
in Table 1. CCDC 981666-981667 contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
7

ACCEPTED MANUSCRIPT
3. Results and discussion
3.1. Preparation of diethylcyanamide and cyanoguanidine complexes
Diethylcyanamide complexes of manganese and rhenium [M(N≡CNEt2)(CO)nL5-n]BPh4 (1a–
5a) were prepared by reacting hydrides MH(CO)nL5-n first with triflic acid (HOTf) and then with an
excess of N≡CNEt2, as shown in Scheme 1.
+
L
M
L
L
M
L
L
M
L
CNEt2
CNEt2
CNEt2
OC
OC
H
OC
OC
OTf
CO
OC
OC
N
HOTf
- H2
exc. N CNEt2
- OTf
-
-
-
OTf
CO
CO
1a, 4a ( I )
+
L
M
L
L
M
L
L
OC
OC
H
L
OC
OC
OTf
L
OC
OC
N
HOTf
- H2
exc. N CNEt2
- OTf
M
OTf
L
L
2a, 5a ( II )
+
+
L
M
L
L
L
M
L
H
L
H
L
L
N
L
HOTf
exc. N CNEt2
- OTf
-
H
L
OTf
M
OTf
OC
OC
L
OC
L
3a ( III )
Scheme 1. M = Mn (1, 2, 3a), Re (4, 5); L = PPh(OEt)2 (1–4), P(OEt)3 (5)
The reaction of the hydride MH(CO)nL5-n (n = 2, 3) with triflic acid is known to proceed with the
formation of dihydrogen complex [M(η2-H2)(CO)nL5-n]+ which, by loss of H2, yields the triflate
intermediate M(κ1-OTf)(CO)nL5-n [18,19]. Substitution of the triflate ligand by N≡CNEt2 afforded
–
the final diethylcyanamide complexes 1a, 2a, 4a, 5a, which were separated as BPh4 salts and
characterised.
The related monocarbonyl MnH(CO)L4 was also reacted with triflic acid to give the stable
dihydrogen cation [Mn(η2-H2)(CO)L4]+ [18], which underwent substitution of the η2-H2 group by
N≡CNEt2 yielding the final diethylcynamide derivative [Mn(N≡CNEt2)(CO)L4]BPh4 (3a).
The related cyanoguanidine complexes [M{N≡CN(H)C(NH2)=NH}(CO)nL5-n]BPh4 (1b–5b)
8

ACCEPTED MANUSCRIPT
were prepared following two different methods involving, in one case, the reaction of hydrides
MH(CO)nL5-n first with an equivalent of triflic acid and then with an excess of cyanamide N≡CNH2,
as shown in Scheme 2.
+
H
N
L
M
L
L
M
L
L
M
L
exc. N CNH2
NH2
C
C
OC
OC
H
OC
OC
OTf
CO
OC
OC
N
HOTf
- H2
-
OTf
+
N
CN C(NH2)2
NH
CO
CO
1b, 4b ( IV )
H
N
L
M
L
L
M
L
L
exc. N CNH2
NH2
C
C
OC
OC
H
L
OC
OC
OTf
L
OC
OC
N
HOTf
- H2
-
M
OTf
N
CN C(NH2)2
NH
L
L
2b, 5b ( V )
Scheme 2. L = M = Mn (1, 2), Re (4, 5); L = PPh(OEt)2 (1, 2, 4), P(OEt)3 (5)
Alternatively, the cyanoguanidine complexes were prepared by reacting hydrides MH(CO)nL5-n first
with HOTf and then with an excess of free cyanoguanidine N≡CN=C(NH2)2 in ethanol.
The formation of complexes 1b, 2b, 4b, 5b from the reaction with cyanamide was not
unexpected, in view of the known ease of dimerisation of N≡CNH2. The initial coordination of
N≡CNH2 to the metal fragment, giving [M(N≡CNH2)(CO)nL5-n]+, may be followed by nucleophilic
attack by a second N≡CNH2 on the cyanamide carbon atom of the coordinate cyanamide yielding,
after H-shift, the N-imine-bonded cyanoguanidine complexes
[M{N(H)=C(NH2)N(H)C≡N}(CO)nL5-n]+. Linkage isomerisation of this ligand gave the final
N-nitrile-bonded derivatives 1b, 2b, 4b, 5b.
Cyanamide and cyanoguanidine complexes of the manganese triad are very rare and, to the
best of our knowledge, only one example of both manganese [11] and rhenium [12]
diethylcyanamide complexes have been reported, and none for cyanoguanidine. The use as
precursors of mixed-ligand hydride complexes MH(CO)nL5-n, containing phosphanes and carbonyls,
allowed easy synthesis of both diethylcyanamide and cyanoguanidine complexes of Mn and Re.
It is worth noting that the cyanamide and cyanoguanidine complexes of both Mn and Re (1–4)
were all prepared with phenyldiethoxyphosphane PPh(OEt)2 as supporting ligand. Instead, rhenium
dicarbonyls [Re(N≡CNEt2)(CO)2L3]BPh4 (5a) and [Re{N(H)=C(NH2)N(H)C≡N}(CO)2L3]BPh4
(5b) were obtained with triethoxyphosphane P(OEt)3 as supporting ligand.
9

ACCEPTED MANUSCRIPT
Complexes 1–5 were all isolated as white or yellow solids stable in air and in solution of polar
organic solvents, where they behave as 1:1 electrolytes [26]. Their characterisation is supported by
analytical and spectroscopic (IR, NMR) data and by X-ray crystal structure determination of
complex [Mn(N≡CNEt2)(CO)2{PPh(OEt)2}3]BPh4 (2a), the ORTEP [27] of which is shown in
Figure 1.
Figure 1. ORTEP view of the cation 2a, drawn at 30% probability level. Phenyl and ethoxy groups
on all the phosphanes were not drawn for clarity.
The compound consists of a tetraphenylborate anion (not shown in figure) and a manganese
cation complex. In the cation, the manganese atom is coordinated by two carbonyl ligands, three
PPh(OEt)2 ligands and a N,N-diethylcyanamide ligand N≡CNEt2. The overall geometry is best
described as octahedral, and the arrangement around the metal is such that the phosphane ligands
are in meridional disposition. Consequently, both carbonyl ligands are cis arranged and the
cyanamide ligand is trans to a carbonyl ligand. Some distortion arises because of the bending of the
mutually trans phosphanes towards the carbonyl ligand, doubtless due to the steric requirements of
the phosphanes. This distortion gives a P-Mn-P trans angle of 170.22(4)º. The other two trans
angles are 178.46(14) and 176.84(10)º, and the cis angles range from 84.21(11) to 95.82(5)º. The
Mn–C carbonyl bond length trans to the phosphane ligand is slightly longer than that trans to the
cyanamide ligand, 1.801(4) Å vs 1.758(3) Å. The Mn–P bond lengths of the mutually phosphane
ligands, 2.2618(18) and 2.2722(17) Å, are slightly shorter than that trans to the carbonyl ligand,
2.2945(19) Å. The Mn–N bond length, 2.002(3) Å, trans to a carbonyl ligand, is longer than that
found in Mn(η5-C5H5)(CO)2(N≡CNEt2), 1.977(2) Å [11]. It is worth noting that such half-sandwich
compound is the first N,N-diethylcyanamide manganese complex to be crystallographically
described1 and, at the moment of writing this paper, there are no others in the CCDC database [28].
10

ACCEPTED MANUSCRIPT
The N,N-diethylcyanamide ligand shows a C(1)-N(1)-Mn bond angle of 175.6(3)º, and a
N(1)-C(1)-N(2) bond angle of 175.5(5)º, matching the sp character of C(1), as confirmed by the
N(1)–C(1) bond length of only 1.133(4) Å, as expected for a triple bond [29]. The N(2)–C(1) bond
length, 1.300(5) Å, matches a double bond length [29] and is similar to that found in other N,N-
diethylcyanamide complexes, for example, Mn(η5-C5H5)(CO)2(N≡CNEt2) [11] or
i
[Ru(NH2 Pr)(NCNEt2){P(OEt)3}4](BPh4)2 [15b]. These values show conjugation between the
nitrogen NEt2 lone pair and the C≡N π bond [1]. It has been stated that η1-bound NCNR2 species
can adopt a bent or linear form in the complexes and that the linear coordination mode (M-N-C
angle of 176–180º) is more common in transition metal complexes. For compound 2a, the angle,
175.5(5)º, falls within the lower limit for linear coordination mode, perhaps due to the trans
coordination of a carbonyl ligand. It is believed that the trans influence enhances the significance of
the bent M-N=C=NEt2 structure (A) shown in Scheme 3 [1,30].
CH2
CH3
CH2
CH3
+
N
N
C
Mn
N
C
N
Mn
CH2
CH3
CH2
CH3
( A )
( B )
Scheme 3.
Also worthy of note is the trigonal planar coordination around the amino N-atom of the
diethylcyanamide ligand [the sum of the angles around N(2) is 357.6°]. This feature has also been
found in Mn(η5-C5H5)(CO)2(N≡CNEt2) [11] and in other dialkylcyanamide complexes, and is
interpreted as a consequence of the delocalisation of the amide lone pair of electrons and the
significant contribution of sp2 hybridised N resonance [1,30,31].
The IR spectra of diethylcyanamide complexes [M(N≡CNEt2)(CO)3{PPh(OEt)2}2]BPh4 (1a,
4a) show a strong band at 2260–2258 cm-1, attributed to the νCN of the nitrile group. In addition, in
the CO stretching region between 2068 and 1942 cm-1, three bands appear – one of medium
intensity and two strong – indicating a mer arrangement of the three carbonyl ligands. In the
temperature range +20 to -80 °C, the 31P NMR spectra show a sharp singlet, indicating the magnetic
equivalence of the two phosphanes. On this basis, mer-trans geometry I (Scheme 1) is proposed for
–
tricarbonyl derivatives 1a and 4a. As well as the signals of the phosphanes and BPh4 anion, the 1H
NMR spectra show a quartet and a triplet of ethyl substituents of cyanamide, matching the proposed
formulation for the complexes.
11

ACCEPTED MANUSCRIPT
Besides the strong νCN band of the N≡CNEt2 group at 2264–2253 cm-1, the IR spectra of
dicarbonyl compounds [M(N≡CNEt2)(CO)2{PPh(OEt)2}3]BPh4 (2a, 5a) show two strong νCO bands
at 1978–1905 and 1897–1892 cm-1, attributed to two carbonyl ligands in a mutually cis position.
The 13C NMR spectrum of 5a also indicates that the two CO groups are not magnetically
equivalent, since they show two triplets of doublets in the carbonyl carbon region, at 193.58 and
191.94 ppm. At 203 K, the 31P NMR spectra of complexes 2a and 5a display an A2B multiplet,
indicating that two phosphanes are magnetically equivalent and different from the third. On this
basis, mer-cis geometry II, like that found in the solid state, is proposed for dicarbonyl derivatives
2a and 5a.
The IR spectrum of the monocarbonyl compound [Mn(N≡CNEt2)(CO){PPh(OEt)2}4]BPh4
(3a) shows νCN at 2253 cm-1 and νCO at 1880 cm-1. The 1H NMR spectrum supports the presence of
the diethylcyanamide ligand, showing the quartet at 2.77 ppm and the triplet at 1.18 ppm of the
ethyl substituents of the cyanamide. In the temperature range +20 to -80 °C, the 31P NMR spectra
show only one singlet, indicating the magnetic equivalence of the four phosphane ligands. On this
basis, trans geometry III (Scheme 1) is proposed for monocarbonyl derivative 3a.
The IR spectra of cyanoguanidine derivatives [M{N≡CN(H)C(NH2)=NH}(CO)3L2]BPh4 (1b,
4b) show the νNH absorptions of the NH and NH2 groups at 3493–3322 cm-1, whereas νCN appears
as one medium-intensity band at 2237–2240 cm-1 for both Mn and Re derivatives. The presence of
only one νCN absorption also indicates that the cyanoguanidine ligand is present in the amine form.
In addition, δNH2 is observed as a strong band at 1632 cm-1 while the CO stretching region has three
bands – one of medium intensity and two strong – also present at 2061–1942 cm-1, indicating a mer
arrangement for the three carbonyl ligands.
–
Besides the characteristic signals of the phosphanes and BPh4 anion, the 1H NMR spectra
show either a broad signal at 3.51 ppm (1b) or two at 4.28 and 4.06 ppm (4b), attributed to the NH2
and NH protons of cyanoguanidine. However, when sample temperature is lowered, the profiles of
the spectra change and, at -70 °C, two broad signals at 3.09 and 2.29 appear for 1b, and at 2.78 and
3.77 ppm, with an intensity ratio of 2:1, for 4b, attributed to the NH2 protons and one NH proton of
cyanoguanidine. The other NH signal is probably masked by the methylene protons of phosphane.
In the temperature range +20 to -70 °C, the 31P NMR spectra show only one singlet, indicating the
magnetic equivalence of the two phosphane ligands. On this basis, mer-trans geometry IV (Scheme
2) is proposed for cyanoguanidine complexes 1b and 4b.
12

ACCEPTED MANUSCRIPT
The IR spectra of dicarbonyl derivatives [M{N≡CN(H)C(NH2)=NH}(CO)2L3]BPh4 (2b, 5b)
show the νNH of the cyanoguanidine at 3529–3344 cm-1, νCN falls to 2247 cm-1 and δNH2 is observed
as a strong band at 1634–1623 cm-1. Two νCO bands also appear at 1981–1967 and 1903–1900 cm-1,
attributed to two carbonyls in mutually cis position.
The 13C NMR spectrum of 2b indicates that the two CO ligands are magnetically non-
equivalent, showing two signals in the carbonyl carbon region at 219.6 and 222.1 ppm. The signals
–
of the phosphanes and BPh4 anion, and a singlet at 58.6 ppm attributed to the resonance of the
C(NH2)=NH group of cyanoguanidine, are also present. The 1H NMR spectra confirm the presence
of the cyanoguanidine ligand showing, at -70 °C, two broad signals at 3.55 and 2.13 ppm (Mn) and
at 4.99 and 4.31 ppm (Re), with an intensity ratio of 1:2, attributed to one NH and the NH2 groups
of the N≡CN(H)C(NH2)=NH ligand. In the temperature range +20 to -80 °C, the 31P spectra show
either an AB2 or A2B multiplet, indicating that two phosphanes are magnetically equivalent and
different from the third. On this basis, mer-cis geometry V (Scheme 2) is proposed for
cyanoguanidine derivatives 2b and 5b.
3.2. Preparation of bis(diethylcyanamide) complexes
Results from the phosphane-carbonyl mixed-ligand fragments M(CO)nL5-n prompted us to
extend study of diethylcyanamide and cyanoguanidine to the simple carbonyl compounds
MBr(CO)5 (M = Mn, Re). The reaction with diethylcyanamide proceeds with substitution of the
carbonyl ligands, giving bis(derivatives) MBr(N≡CNEt2)2(CO)3 (6a, 7a), which were isolated in
good yield and characterised (Scheme 4).
Br
Br
CNEt2
OC
OC
CO
CO
OC
OC
N
N
exc. N CNEt2
toluene
M
M
CNEt2
CO
CO
6a, 7a ( VI )
Scheme 4. M = Mn (6a), Re (7a).
Although the reaction proceeded at room temperature with manganese, reflux conditions were
required for rhenium. However, only bis(diethylcyanamide) complexes 6a and 7a were obtained
from this reaction: the addition of an equimolar amount of N≡CNEt2 did not yield monocyanamide
derivatives of the type MBr(N≡CNEt2)(CO)4, but a mixture of bis-complexes 6a and 7a and the
starting MBr(CO)5 compounds. It is probable that substitution of one carbonyl in the
13

ACCEPTED MANUSCRIPT
monocyanamide species MBr(N≡CNEt2)(CO)4 is faster than that in MBr(CO)5, mainly yielding bis-
ones MBr(N≡CNEt2)2(CO)3. In addition, reflux conditions for Mn, or longer reaction times for Re,
did not afford any tris(cyanamide) MBr(N≡CNEt2)3(CO)2 species, but only mixtures of bis-
complexes and decomposition products. Pentacarbonyl compounds MBr(CO)5 were also treated
with both cyanamide N≡CNH2 and cyanoguanidine, but no pure compounds resulted, the isolated
products being intractable mixtures. Therefore, it seems that only bis(diethylcyanamide) complexes
6a and 7a can be obtained from the reaction of MBr(CO)5 with cyanamide.
Bis(cyanamide) complexes of transition metals are very rare [5c,6c,32] and involve only Pt
[6c,32a,b], Ru [32c] and Cu [5c] derivatives. The reaction of pentacarbonyl compounds MBr(CO)5
with diethylcyanamide allows the preparation of the first examples of bis(cyanamide) derivatives of
the manganese triad.
Complexes MBr(N≡CNEt2)2(CO)3 (6a, 7a) were isolated as pale-yellow (6a) or white (7a)
solids, stable in air and in solution of common organic solvents, where they behave as non-
electrolytes [26]. Their formulation is supported by analytical and spectroscopic (IR, NMR) data
and by X-ray crystal structure determination of complex ReBr(N≡CNEt2)2(CO)3 (7a), the ORTEP
[27] of which is shown in Figure 2.
Figure 2. ORTEP view of 7a drawn at 30% probability level. Phenyl and ethoxy groups on all the
phosphanes were not drawn for clarity.
The compound consists of a rhenium atom coordinated by one bromine ligand, three carbonyl
ligands, and two N,N-diethylcyanamide ligands. The overall geometry is best described as
octahedral, and the arrangement around the metal is such that the carbonyl ligands are in facial
14

ACCEPTED MANUSCRIPT
disposition. Consequently, both cyanamide ligands are cis-disposed. The Re–C carbonyl bond
distances are in the range 1.903(4) to 1.917(4) Å, the shorter one corresponding to that which is
trans to the bromine ligand, but they do not show significant differences. The trans influence of the
cyanamide ligand is comparable with the σ-donor bromine ligand, as previously reported [12,33].
The Re–Br bond length, 2.6191(5) Å, is close to the mean value found in the CCDC database [34].
To the best of our knowledge [28], only one cyanamide rhenium complex has been
crystallographically described, the already-mentioned Re(II) complex mer-
ReCl2(NCNEt2)(PMePh2)3 [12]. The latter has a Re–N distance of 2.109(5) Å, trans to a phosphane
ligand. Complex 7a shows two Re–N(cyanamide) bond lengths of 2.142(3) and 2.138(3) Å, trans to
a carbonyl ligand. Although these values are longer than that of the Re(II) complex mer-
ReCl2(NCNEt2)P3, they are comparable to other trans carbonyl-nitrile Re(I) complexes, like the
values of 2.145(7) Å in [Re(N,N’-terpy)(CO)3(CH3CN)]PF6 [35] or 2.151(7) Å in
[Re(CO)3(CH3CN){H(pzAnMe)}]PF6 [36].
As in 2a (see above) or other N,N-diethylcyanamide complexes [1,15b] these ligands have
average C-N-Re bond angles of 172.7(3)º and a N-C-N bond angles of 177.5(4)º. Again, the
cyanamide moiety shows extensive electronic delocalisation, and the C–N bond lengths
alternatively match triple [1.146(5), 1.148(5) Å] and double bonds [1.304(5), 1.308(5) Å]. The
amine nitrogen atoms also display a distorted trigonal-planar geometry, as demonstrated by the sum
of angles of 356.5(3) and 359.5(3)º. It is worth noting that, in the Re(II) compound mer-
ReCl2(NCNEt2)(PMePh2)3 [12] the coordination around this atom is described as trigonal-
pyramidal.
The average C-N-Re bond angles of 172.7(3)º [171.8(3) and 173.6(3)º] lie both out of the
range (180–176º) proposed for linear arrangement and out of the values proposed for bent
coordination (M–N–C ≤ 170º), being more acute than the value found for the Re(II) compound mer-
ReCl2(NCNEt2)(PMePh2)3 [12], 174.3(6)º. Again as in 2a, the trans influence of the carbonyl
groups may explain this bending.
In the carbonyl stretching region, the IR spectra of bis(diethylcyanamide) complexes
MBr(N≡CNEt2)2(CO)3 (6a, 7a) show three strong bands at 2033, 1930 and 1910 cm-1 (6a) and
2023, 1917 and 1897 cm-1 (7a), indicating a fac arrangement of the carbonyl ligands. A strong band
at 2264 cm-1 also appears in the spectra of 6a and 7a, and was attributed to the νCN of the
diethylcyanamide ligand. The presence of only one band is rather surprising, as the two cyanamides
must be in mutually cis position and should thus show two νCN bands. The νCN values of the cis
15

ACCEPTED MANUSCRIPT
cyanamides are probably so close that the instrument could only detect one slightly broad signal.
The 1H NMR spectra of 6a and 7a confirm the presence of the diethylcyanamide ligands, showing
one quartet at 3.19–3.17 ppm and one triplet at 1.33–1.32 ppm of their ethyl substituents. The
presence of only a single signal (one quartet and one quintet) indicates the magnetic equivalence of
the two N≡CNEt2 ligands. On this basis, fac geometry VI, like that found in the solid state for 7a,
may be proposed in solution for the bis(diethylcyanamide) derivatives 6a and 7a.
In ethanol solution containing NaBPh4, complex fac-ReBr(N≡CNEt2)2(CO)3 (7a) slowly
isomerised to give the mer-cis derivative 7a1, which was isolated as a white solid and characterised
(Scheme 5).
Br
CO
CNEt2
CNEt2
OC
OC
N
N
OC
Br
N
N
EtOH
Re
Re
NaBPh4
CNEt2
CNEt2
CO
CO
fac-7a
mer-cis-7a1 ( VII )
Scheme 5.
Crucial for the fac-mer isomerisation of 7 was the presence of the NaBPh4 salt which, by rendering
the bromide ligand labile, may favour rearrangement of the ligands. This isomerisation is not
surprising, owing to the large number of known rhenium complexes having mer geometry [37].
The IR spectrum of 7a1 shows three νCO bands, one of medium intensity at 2034 cm-1 and two
strong ones at 1928 and 1872 cm-1, indicating a mer arrangement of of the three carbonyl groups.
The spectrum also displays a band of medium intensity at 2264 cm-1, attributed to the νCN of the
diethylcyanamide ligands. The presence of these ligands was confirmed by the 1H NMR spectrum,
which shows two quartets at 3.11 and 3.02 ppm and two triplets at 1.27 and 1.23 ppm of the ethyl
substituents of N≡CNEt2. Such a pattern also indicates that the two cyanamide ligands are
magnetically non-equivalent. On this basis, mer-cis geometry VII is proposed for complex 7a1. As
observed in the related complex 7a, the presence of only one νCN band for two N≡CNEt2 groups in
mutually cis position may be because the two νCN have such close values that only a single band is
visible in the spectrum.
4. Conclusions
In this report we describe the preparation of diethylcyanamide and cyanoguanidine complexes
16

ACCEPTED MANUSCRIPT
of manganese and rhenium stabilised by the mixed-ligand fragment M(CO)nL5-n, containing
phosphanes and carbonyls as supporting groups. The synthesis of the first bis(diethylcyanamide)
derivatives MBr(N≡CNEt2)2(CO)3 of manganese and rhenium is reported. The structural parameters
of both mono- and bis(diethylcyanamide) complexes were also determined.
Acknowledgment. Thanks go to Mrs. Daniela Baldan for technical assistance.
References and Notes
[1] N.A. Bokach, V.Yu. Kukushkin, Coord. Chem. Rev. 257 (2013) 2293–2316.
[2] H. Bock, Angew. Chem., Int. Ed. Engl. 1 (1962) 550.
[3] E.O. Fischer, W. Kleine, U. Schubert, D. Neugebauer, J. Organomet. Chem. 149 (1978) C40–
C42.
[4] M.H. Chisholm, J.C. Huffman, N.S. Marchant, J. Am. Chem. Soc. 105 (1983) 6162–6163.
[5] (a) M.S. Begley, P. Hubberstey, P.H. Walton, J. Chem. Soc., Dalton Trans. (1995) 957–962;
(b) A.S. Batsanov, P. Hubberstey, C.E. Russel, P.H. Walton, J. Chem. Soc., Dalton Trans.
(1997) 2667–2672;
(c) A.S. Batsanov, M.S. Begley, W.W. George, P. Hubberstey, M. Munakata, C.E. Russel,
P.H. Walton, J. Chem. Soc., Dalton Trans. (1999) 4251–4259;
(d) J.K. Bera, M. Nethaji, A.G. Samuelson, Inorg. Chem. 38 (1999) 1725–1735;
(e) S.-M. Kuang, D.G. Cuttell, D.R. McMillin, P.E. Fanwick, R.A. Walton, Inorg. Chem. 41
(2002) 3313–3322;
(f) L.-L. Zheng, J.-D. Leng, W.-T. Liu, W.-X. Zhang, J.-X. Lu, M.-L. Tong, Eur. J. Inorg.
Chem. (2008) 4616–4624;
(g) H. Hadadzadeh, A.R. Rezvani, H. Esfandiari, Polyhedron 27 (2008) 1809–1817;
(h) L.-C. Kang, X. Chen, X.-S. Wang, Y.-Z. Li, Y. Song, J.-L. Zuo, X.-Z. You, Dalton Trans.
40 (2011) 5200–5209.
[6] (a) M.F.C. Guedes da Silva, E.M.P.R.P. Branco, Y. Wang, J.J.R. Fraústo da Silva, A.J.L.
Pombeiro, R. Bertani, R.A. Michelin, M. Mozzon, F. Benetollo, G. Bombieri, J. Organomet.
Chem. 490 (1995) 89–99;
(b) M.F.C. Guedes da Silva, C.M.P. Ferreira, E.M.P.R.P. Branco, J.J.R. Fraústo da Silva,
A.J.L. Pombeiro, R.A. Michelin, U. Belluco, R. Bertani, M. Mozzon, G. Bombieri, F.
Benetollo, V.Yu. Kukushkin, Inorg. Chim. Acta 265 (1997) 267–270;
17

ACCEPTED MANUSCRIPT
(c) C.M.P. Ferreira, M.F.C. Guedes da Silva, J.J.R. Fraústo da Silva, A.J.L. Pombeiro, V.Yu.
Kukushkin, R.A. Michelin, Inorg. Chem. 40 (2001) 1134–1142;
(d) C.M.P. Ferreira, M.F.C. Guedes da Silva, T. Duarte, J.J.R. Fraústo da Silva, A.J.L.
Pombeiro, R.A. Michelin, V.Yu. Kukushkin, Inorg. Chim. Acta 334 (2002) 395–402;
(e) C.M.P. Ferreira, M.F.C. Guedes da Silva, R.A. Michelin, V.Yu. Kukushkin, J.J.R. Fraústo
da Silva, A.J.L. Pombeiro, Dalton Trans. (2003) 3751–3756;
(f) A.G. Tskhovrebov, N.A. Bokach, M. Haukka, V.Yu. Kukushkin, Inorg. Chem. 48 (2009)
8678–8688;
(g) M.N. Kopylovich, J. Lasri, M.F.C. Guedes da Silva, A.J.L. Pombeiro, Eur. J. Inorg.
Chem. (2011) 377–383.
[7] (a) S.M.P.R.M. Cunha, M.F.C. Guedes da Silva, A.J.L. Pombeiro, J. Chem. Soc., Dalton
Trans. (2002) 1971–1979;
(b) L.M.D.R.S. Martins, E.C.B.A. Alegria, D.L. Hughes, J.J.R. Fraústo da Silva, A.J.L.
Pombeiro, Dalton Trans. (2003) 3743–3750;
(c) S.M.P.R.M. Cunha, M.F.C. Guedes da Silva, A.J.L. Pombeiro, Inorg. Chem. 42 (2003)
2157–2164;
(d) Y.-L. Tsai, F.H. Stephens, K. Meyer, A. Mendiratta, M.D. Gheorghiu, C.C. Cummins,
Organometallics 22 (2003) 2902–2913.
[8] (a) A. Schäfer, E. Herdtweck, G.D. Frey, Inorg. Chim. Acta 359 (2006) 4885–4890;
(b) Y. Tanaka, H. Kojitani, M. Iwasaki, Y. Ishii, Dalton Trans. (2007) 4701–4707;
(c) K. Fukumoto, T. Oya, M. Itazaki, H. Nakazawa, J. Am. Chem. Soc. 131 (2009) 38–39;
(d) J. Xiang, W.-L. Man, S.-M. Yiu, S.-M. Peng, T.-C. Lau, Chem. Eur. J. 17 (2011) 13044–
13051;
(e) C. Harb, P. Kravtsov, M. Choudhuri, E.R. Sirianni, G.P.A. Yap, A.B.P. Lever, R.J.
Crutchley, Inorg. Chem. 52 (2013) 1621–1630.
[9] (a) R.A. Michelin, M. Mozzon, R. Bertani, Coord. Chem. Rev. 147 (1996) 299–338;
(b) V.Yu. Kukushkin, A.J.L. Pombeiro, Chem. Rev. 102 (2002) 1771–1802.
[10] A.J.L. Pombeiro, V.Yu. Kukushkin, in Comprehensive Coordination Chemistry, 2nd edn.;
McCleverty, J. A.; Meyer, T. J., Eds.; Elsevier Science: New York, 2004, vol. I.
[11] A. Schäfer, E. Herdtweck, G.D. Frey, Inorg. Chim. Acta 359 (2006) 4885–4890.
[12] M.T.A.R.S. Costa, J.J.R. Frausto da Silva, A.J.L. Pombeiro, R.A. Michelin, G. Bombieri, F.
Benetollo, Inorg. Chim. Acta 280 (1998) 308–315.
18

ACCEPTED MANUSCRIPT
[13] (a) G. Albertin, S. Antoniutti, L. Bonaldo, A. Botter, J. Castro, Inorg. Chem. 52 (2013) 2870–
2879;
(b) G. Albertin, S. Antoniutti, J. Castro, J. Organomet. Chem. 697 (2012) 6–14;
(c) G. Albertin, S. Antoniutti, G. Zanardo, J. Organomet. Chem. 692 (2007) 3706–3717;
(d) G. Albertin, S. Antoniutti, A. Bacchi, A. Celebrin, G. Pelizzi, G. Zanardo, Dalton Trans.
(2007) 661–668;
(e) G. Albertin, S. Antoniutti, M. Bedin, J. Castro, S. Garcia-Fontán, Inorg. Chem. 45 (2006)
3816–3825;
(f) G. Albertin, S. Antoniutti, A. Bacchi, F. De Marchi, G. Pelizzi, Inorg. Chem. 44 (2005)
8947–8954;
(g) G. Albertin, S. Antoniutti, M. Bortoluzzi, J. Castro-Fojo, S. Garcia-Fontán, Inorg. Chem.
43 (2004) 4511–4522;
(h) G. Albertin, S. Antoniutti, A. Bacchi, B. Fregolent, G. Pelizzi, Eur. J. Inorg. Chem. (2004)
1922–1938.
[14] (a) G. Albertin, S. Antoniutti, S. Beraldo, F. Chimisso, Eur. J. Inorg. Chem. (2003) 2845–
2854;
(b) G. Albertin, S. Antoniutti, A. Bacchi, M. Bergamo, E. Bordignon, G. Pelizzi, Inorg.
Chem. 37 (1998) 479–489;
(c) G. Albertin, S. Antoniutti, A. Bacchi, E. Bordignon, P. M. Dolcetti, G. Pelizzi, J. Chem.
Soc., Dalton Trans. (1997) 4435–4444.
[15] (a) G. Albertin, S. Antoniutti, J. Castro, Eur. J. Inorg. Chem. (2009) 5352–5357;
(b) G. Albertin, S. Antoniutti, A. Caia, J. Castro, Dalton Trans. 43 (2014) 7314–7323.
[16] R. Rabinowitz, J. Pellon, J. Org. Chem. 26 (1961) 4623–4626.
[17] G. Balacco, http://www.inmr.net/
[18] G. Albertin, S. Antoniutti, M. Bettiol, E. Bordignon, F. Busatto, Organometallics 16 (1997)
4959–4969.
[19] G. Albertin, S. Antoniutti, S. Garcia-Fontán, R. Carballo, F. Padoan, J. Chem. Soc., Dalton
Trans. (1998) 2071–2081.
[20] SMART Version 5.054, Instrument control and data collection software, Bruker Analytical X-
ray Systems Inc., Madison, Wisconsin, USA, 1997.
[21] SAINT Version 6.01, Data Integration software package, Bruker Analytical X-ray Systems
Inc., Madison, Wisconsin, USA, 1997.
19

ACCEPTED MANUSCRIPT
[22] G.M. Sheldrick, SADABS. A Computer Program for Absorption Corrections, University of
Göttingen, Germany, 1996.
[23] P. McArdle, J. Appl. Cryst. 28 (1995) 65–65.
[24] G.M. Sheldrick, Acta Crystallogr. A64 (2008) 112–122.
[25] A.S. Kritchenkov, N.A. Bokach, M. Haukka, V.Yu. Kukushkin, Dalton Trans. 40 (2011)
4175–4182.
[26] W.J. Geary, Coord. Chem. Rev. 7 (1971) 81–172.
[27] L.J. Farrugia, J. Appl. Cryst. 30 (1997) 565–565.
[28] CCDC Database, CSD version 5.34 (May 2013 updated).
[29] A.G. Orpen, L. Brammer, F.H. Allen, O. Kennard, D.G. Watson, R. Taylor, J. Chem. Soc.,
Dalton Trans. (1989) S1–S83.
[30] T.B. Anisimova, N.A. Bokach, I.O. Fritsky, M. Haukka, J. Mol. Struct. 1005 (2011) 141–143.
[31] P. Achord, E. Fujita, J.T. Muckerman, B. Scott, G.C. Fortman, M. Temprado, X. Cai, B.
Captain, D. Isrow, J.J. Weir, J.E. McDonough, C.D. Hoff, Inorg. Chem. 48 (2009) 7891–
7904.
[32] (a) N.A. Bokach, T.B. Pakhomova, V.Yu. Kukushkin, M. Haukka, A.J.L. Pombeiro, Inorg.
Chem. 42 (2003) 7560–7568;
(b) P.V. Gushchin, N.A. Bokach, M. Haukka, E.S. Dmitrieva, V.Yu. Kukushkin, Acta Cryst.
E62 (2006) M244–M246;
(c) D.S. Pandey, A. Mishra, U.C. Agarwala, Inorg. Chim. Acta 172 (1990) 13–18.
[33] M.-N. Ohnet, A. Spasojević-de Biré, N.Q. Dao, P. Schweiss, M. Braden, H. Fischer, D.
Reindl, J. Chem. Soc., Dalton Trans. (1995) 665–672.
[34] A search in the CCDC Database, CSD version 5.34 (May 2013 updated) gives 357 fac-
tricarbonylbromorhenium compounds, and the mean value for Re–Br bond length is 2.628(24)
Å, and the Br-Re-C angle 176.2(20)º.
[35] A.J. Amoroso, A. Banu, M.P. Coogan, P.G. Edwards, G. Hossain, K.M.A. Malik, Dalton
Trans. 39 (2010) 6993–7003.
[36] B.J. Liddle, S. Wanniarachchi, S.V. Lindeman, J.R. Gardinier, J. Organomet. Chem. 695
(2010) 53–61.
[37] (a) G. Albertin, S. Antoniutti, J. Castro, S. García-Fontán, G. Zanardo, Organometallics 26
(2007) 2918–2930;
(b) G. Albertin, S. Antoniutti, M.T. Giorgi, Eur. J. Inorg. Chem. (2003) 2855–2866;
20

ACCEPTED MANUSCRIPT
(c) G. Albertin, S. Antoniutti, S. García-Fontán, R. Carballo, F. Padoan, J. Chem. Soc., Dalton
Trans. (1998) 2071–2081.
21

ACCEPTED MANUSCRIPT
Table 1. Crystal data and structure refinement for complexes 2a and 7a.
Identification code
Empirical formula
Formula weight
Temperature
2a
7a
C61H75BMnN2O8P3
1122.89
293(2) K
C13H20BrN4O3Re
546.44
100(2) K
Wavelength
Crystal system
Space group
0.71073 Å
Triclinic
P-1
0.71073 Å
Monoclinic
C2/c
Unit cell dimensions
a = 11.114(10) Å
b = 15.082(14) Å
c = 18.021(16) Å
α = 86.985(14)º
β = 84.740(14)º
γ = 82.889(16)º
2982(5) Å3
2
a = 17.461(3) Å
b = 16.463(3) Å
c = 14.343(2) Å
α = 90°
β = 119.469(2)°
γ = 90°
Volume
Z
Density (calculated)
Absorption coefficient
F(000)
3589.6(10) Å3
8
1.251 Mg/m3
0.356 mm-1
1188
2.022 Mg/m3
9.012 mm-1
2080
Crystal size
Θ range for data collection
Index ranges
0.46 × 0.41 × 0.29 mm
2.26 to 25.69º
-13 ≤ h ≤ 13
-17 ≤ k ≤ 18
-21 ≤ l ≤ 21
43956
0.38 × 0.15 × 0.09 mm
1.82 to 27.99°
-23 ≤ h ≤ 22
-21 ≤ k ≤ 21
-18 ≤ l ≤ 18
16193
Reflections collected
Independent reflections
Reflections observed (>2σ) 7506
11063 [R(int) = 0.0397]
4285 [R(int) = 0.0472]
3551
Data Completeness
0.975
0.989
Absorption correction
Max. and min. transmission 0.7452 and 0.7052
Refinement method
Semi-empirical from equivalentsSemi-empirical from equivalents
0.4038 and 0.1879
Full-matrix least-squares on F2 Full-matrix least-squares on F2
Data / restraints / parameters 11063 / 2 / 692
4285 / 0 / 212
1.035
Goodness-of-fit on F2
1.020
Final R indices [I>2σ(I)]
R1 = 0.0488
R1 = 0.0247
wR2 = 0.1160
R1 = 0.0845
wR2 = 0.0548
R1 = 0.0367
R indices (all data)
wR2 = 0.1438
wR2 = 0.0600
Largest diff. peak and hole
0.801 and -0.777 e Å-3
1.765 and -2.211 e Å-3
22

ACCEPTED MANUSCRIPT
Table 2. Bond lengths [Å] and angles [º] for 2a.
Mn–N(1)
Mn–P(2)
2.002(3)
2.2618(18)
1.758(3)
1.133(4)
1.356(8)
1.274(8)
1.154(4)
Mn–P(1)
Mn–P(3)
Mn–C(7)
C(1)–N(2)
N(2)–C(2)
C(4)–C(5)
C(7)–O(7)
2.2945(19)
2.2722(17)
1.801(4)
1.300(5)
1.572(8)
Mn–C(6)
N(1)–C(1)
N(2)–C(4)
C(2)–C(3)
C(6)–O(6)
1.390(12)
1.138(4)
N(1)-Mn-P(1)
N(1)-Mn-C(6)
N(1)-Mn-C(7)
P(2)-Mn-C(6)
P(3)-Mn-C(6)
N(1)-Mn-P(3)
C(6)-Mn-P(1)
P(3)-Mn-P(1)
N(1)-C(1)-N(2)
C(1)-N(2)-C(2)
C(3)-C(2)-N(2)
Mn-C(6)-O(6)
85.30(10)
178.46(14)
92.17(14)
91.19(12)
86.94(12)
92.83(10)
93.21(13)
95.82(5)
175.5(5)
115.5(5)
119.5(7)
178.1(3)
P(1)-Mn-P(2)
N(1)-Mn-P(2)
C(6)-Mn-C(7)
P(2)-Mn-C(7)
P(3)-Mn-C(7)
P(2)-Mn-P(3)
C(7)-Mn-P(1)
C(1)-N(1)-Mn
C(1)-N(2)-C(4)
C(4)-N(2)-C(2)
N(2)-C(4)-C(5)
Mn-C(7)-O(7)
93.86(5)
89.28(9)
89.34(16)
84.21(11)
86.17(11)
170.22(4)
176.84(10)
175.6(3)
125.0(6)
117.1(6)
116.7(8)
176.8(3)
23

ACCEPTED MANUSCRIPT
Table 3. Bond lengths [Å] and angles [º] for 7a.
Re–C(1)
Re–C(3)
Re–N(11)
C(1)–O(1)
1.917(4)
1.906(4)
2.142(3)
1.140(5)
1.154(5)
1.304(5)
1.480(5)
1.465(12)
1.148(5)
1.476(5)
1.500(6)
Re–C(2)
Re–Br
Re–N(21)
C(2)–O(2)
N(11)–C(11)
N(12)–C(12)
C(12)–C(13)
C(14)–C(15B)
C(21)–N(22)
N(22)–C(24)
C(24)–C(25)
1.903(4)
2.6191(5)
2.138(3)
1.149(5)
1.146(5)
1.476(5)
1.499(6)
1.329(17)
1.308(5)
1.476(5)
1.505(6)
C(3)–O(3)
C(11)–N(12)
N(12)–C(14)
C(14)–C(15A)
N(21)–C(21)
N(22)–C(22)
C(22)–C(23)
C(1)-Re-C(2)
C(1)-Re-C(3)
C(3)-Re-N(21)
C(2)-Re-N(11)
C(1)-Re-N(11)
C(2)-Re-Br
C(1)-Re-Br
N(11)-Re-Br
O(2)-C(2)-Re
C(11)-N(11)-Re
C(11)-N(12)-C(12)
C(12)-N(12)-C(14)
C(21)-N(22)-C(22)
C(22)-N(22)-C(24)
90.23(18)
86.16(16)
177.35(14)
94.93(16)
174.81(15)
176.47(12)
91.57(12)
83.25(9)
178.4(4)
171.8(3)
120.6(3)
119.6(3)
C(2)-Re-C(3)
88.75(16)
93.32(15)
95.48(14)
94.54(14)
83.64(12)
94.40(11)
83.48(9)
176.7(4)
177.4(3)
178.0(5)
119.3(3)
173.6(3)
177.0(4)
118.5(3)
C(2)-Re-N(21)
C(1)-Re-N(21)
C(3)-Re-N(11)
N(21)-Re-N(11)
C(3)-Re-Br
N(21)-Re-Br
O(1)-C(1)-Re
O(3)-C(3)-Re
N(11)-C(11)-N(12)
C(11)-N(12)-C(14)
C(21)-N(21)-Re
N(21)-C(21)-N(22)
C(21)-N(22)-C(24)
119.0(3)
119.0(3)
24

ACCEPTED MANUSCRIPT
G
R A P H I C A L
A
B S T R A C T
H
+
N
+
L
L
M
L
Br
M
NH2
CNEt2
C
CNEt2
CNEt2
C
(L)OC
OC
N
(L)OC
OC
N
OC
OC
N
N
M
L
CO(L)
CO(L)
NH
CO
M = Mn, Re; L = PPh(OEt)2
The preparation of diethylcyanamide and cyanoguanidine complexes of manganese and rhenium is
described. The first example of bis(diethylcyanamide) complexes of these metals is also reported.
25